Heterocyclic Amido Transition Metal Complexes, Production and Use Thereof

ABSTRACT

Heterocyclic amido transition metal complexes are disclosed for use in alkene polymerization to produce polyolefins, preferably multimodal polyolefins. The heterocyclic amido transition metal complexes are formed by the chelation of a tridentate dianionic heterocyclic amido ligand to a group 3, 4, or 5 transition metal, where the tridentate ligand coordinates to the metal forming a five-membered ring and an eight-membered ring.

PRIORITY CLAIM

The present application claims priority to and the benefit of U.S. Ser.No. 62/368,511, filed Jul. 29, 2016 and is incorporated by reference inits entirety.

FIELD OF THE INVENTION

The invention relates to heterocyclic amido transition metal complexesand intermediates and processes for use in making such heterocyclicamido complexes. The transition metal complexes may be used as catalystsfor alkene polymerization processes.

BACKGROUND OF THE INVENTION

Pyridyl amines have been used to prepare Group 4 complexes which areuseful transition metal components in the polymerization of alkenes, seefor example, US 2002/0142912, U.S. Pat. No. 6,900,321, and U.S. Pat. No.6,103,657, where the ligands have been used in complexes in which theligands are coordinated in a bidentate or tridentate fashion to thetransition metal atom, wherein the pyridylamide ligand is chelated tothe transition metal with the formation of five membered rings.

Davies and Solan describe in WO 2005/095469 catalyst compounds that usetridentate ligands through two nitrogen atoms (one amido and onepyridyl) and one oxygen atom, wherein the tridentate ligand is chelatedto the transition metal with the formation of five and six memberedrings.

US 2004/0220050 A1 and WO 2007/067965 disclose complexes in which theligand is coordinated in a tridentate fashion through two nitrogen (oneamido and one pyridyl) and one carbon (aryl anion) donors, wherein thepyridylamide ligand is chelated to the transition metal with theformation of five membered rings.

The above mentioned pyridyl amide complexes are known to undergoinsertion of an alkene into the metal-aryl bond of the catalystprecursor during activation (Froese, R. D. J. et al., J. Am. Chem. Soc.2007, 129, 7831-7840) to form an active catalyst that has a tridentateligand chelated to the transition metal with five and seven memberedrings.

Kuhlman and Whiteker disclose in US 2010/0227990 pyridylamide complexesin which the ligand is chelated in a tridentate fashion through twonitrogen (one amido and one pyridyl) and one carbon (alkyl anion)donors, with the formation of five and seven membered rings.

WO 2010/037059 discloses pyridine containing amines for use inpharmaceutical applications.

U.S. Pat. No. 7,973,116 and US 2011/0224391 describe pyridyldiamidecomplexes in which the ligand is chelated in a tridentate fashionthrough three nitrogen donors (two amido and one pyridyl), with theformation of five and seven membered rings.

WO 2007/130307 describes hafnium complexes of heterocyclic ligands inwhich the ligand is chelated in a tridentate fashion through twonitrogen (one amido and one heterocyclic Lewis base) and one carbon(aryl anion) donor, with the formation of five and six membered rings.

Other references of interest include: 1) Domski, G. J.; Rose, J. M.;Coates, G. W.; Bolig, A. D.; Brookhart, M. “Living alkenepolymerization: New methods for the precision synthesis of polyolefins”Prog. Polym. Sci. 2007, 32, 30-92; 2) Giambastiani, G.; Laconi, L.;Kuhlman, R. L.; Hustad, P. D “Imino- and amido-pyridinate d-block metalcomplexes in polymerization/oligomerization catalysis” Chapter 5 inOlefin Upgrading Catalysis by Nitrogen -based Metal Complexes I,Catalysis by Metal Complexes, Springer, 2011; 3) Vaughan, A; Davis, D.S.; Hagadorn, J. R. in Comprehensive Polymer Science, Vol. 3, Chapter20, “Industrial catalysts for alkene polymerization”, 2012; 4) Gibson,V. C.; Spitzmesser, S. K. Chem. Rev. 2003, 103, 283; 5) Britovsek, G. J.P.; Gibson, V. C.; Wass, D. F. Angew. Chem. Int. Ed. 1999, 38, 428; 6)Inorganic Chemistry (2010) 49, (11), 5143-5156; 7) JACS, (1997) 119(14),3411-3412; 8) Organometallics, (1997) 16(26), 5857-5868; 9)Organometallics, (1998), 17(3), 466-474; and 10) Inorganica ChimicaActa, (1997), 263(1-2), 287-299.

There still is need for new catalysts complexes with enhancedperformance in alkene polymerization.

Further, there is a need in the art for new catalysts with no symmetry(i.e., C₁ point group symmetry) that can polymerize alpha olefins toyield crystalline polymers.

SUMMARY OF THE INVENTION

New catalyst compositions for olefin polymerizations are describedherein featuring a group 3, 4, or 5 metal bound to a tridentatedianionic ligand that chelates to the metal center with a five-memberedring and an eight-membered ring. These novel catalyst compositions areshown herein to be active for olefin polymerization, especially forpreparation of polymers containing ethylene.

This invention relates to novel transition metal complexes of dianionictridentate ligands containing at least one amido donor group, whereinthe tridentate ligand chelates to the metal in such a manner to formboth five- and eight-membered rings. This invention also relates toheterocyclic amido transition metal complexes represented by the formula(A), (B), (C), or (D):

-   wherein:-   M is a Group 3, 4, or 5 metal;-   Q¹ is a group that links R² and R³ by a three atom bridge    represented by the formula:-   -G¹-G²-G³- where G² is a group 15 or 16 atom that forms a dative    bond to M, G¹ and G³ are each a group 14 atom that are joined    together by two or three additional group 14, 15, or 16 atoms to    form a heterocycle or substituted heterocycle;-   Q² is a group that forms an anionic bond with M, said Q² group being    selected from O, S, CH₂, CHR¹⁷, C(R¹⁷)₂, NR¹⁷, or PR¹⁷, where each    R¹⁷ is independently selected from hydrogen, halogen, hydrocarbyls,    substituted hydrocarbyls, halocarbyls, substituted halocarbyls,    silylcarbyls, and polar groups;-   Q²′ is a group that forms an anionic bond with M, said Q²′ group    being selected from N, P, CH, or CR¹⁷ where R¹⁷ is defined as above;-   Q³ is -(T-T)- or -(T-T-T)-, where each T is a substituted or    unsubstituted group 14, 15, or 16 element so that together with the    “—C—N═C—” fragment it forms a 5- or 6-membered heterocycle or    substituted heterocycle;-   R¹ is selected from hydrocarbyls, substituted hydrocarbyls,    halocarbyls, substituted halocarbyls, and silylcarbyls;

R² is —E(R¹²)(R¹³)— where E is carbon, silicon, or germanium, and eachR¹² and R¹³ is independently selected from the group consisting ofhydrogen, halogen, hydrocarbyls, substituted hydrocarbyls, halocarbyls,substituted halocarbyls, silylcarbyls, and polar groups; R³ is either Cor N, and R⁴ and R⁵ are C, and R³ and R⁴ are part of a five orsix-membered carbocyclic or heterocyclic ring, which may be substitutedor unsubstituted, and R⁴ and R⁵ are part of a five or six-memberedcarbocyclic or heterocyclic ring, which may be substituted orunsubstituted;

-   each J is independently selected from C, CH, CH₂, CR¹⁸, CHR¹⁸,    C(R¹⁸)₂, Si(R¹⁸)₂, SiH(R¹⁸), NH, NR¹⁸, O, or S, where R¹⁸ is    selected from hydrocarbyls, substituted hydrocarbyls, halocarbyls,    substituted halocarbyls, halogen, and silylcarbyls;-   each x is independently 3 or 4 representing the number of J groups    linked together in series; Y is selected from substituted and    unsubstituted group 14 elements including, but not limited to CH₂,    CH(R¹⁸), C(R¹⁸)₂, C(O), and C(NR¹⁸), where R¹⁸ is defined as above,    and wherein the heteroatom (such as O or N) is optionally bonded to    M;-   Y′ is selected from substituted and unsubstituted group 14 elements    including, but not limited to CH, C(R¹⁸), where R¹⁸ is defined as    above;-   L is an anionic leaving group, where the L groups may be the same or    different and any two L groups may be linked to form a dianionic    leaving group;-   L′ is neutral Lewis base;-   n is 1, 2, or 3;-   w is 0, 1, 2, or 3;-   wherein n+w is not greater than 4;-   wherein the tridentate dianionic ligand is chelated to the metal M    in such a fashion that the complex features an eight-membered ring    and a five-membered ring, which are indicated in the formulas (A)    through (D) by the numbers 8 and 5, respectively.

This invention further relates to a process to make the above complex,process to make intermediates for the above complex and methods topolymerize olefins using the above complex.

This invention further relates to process to a polymerization process toproduce polyolefin comprising contacting one or more olefin monomerswith a catalyst system comprising the catalyst compounds describedherein and activator, and obtaining polymer (such as by recovery processusing liquid-solid, liquid-liquid, vapor-liquid, or vapor-solidseparations) olefin polymer.

DETAILED DESCRIPTION OF THE INVENTION

The specification describes transition metal complexes. The term complexis used to describe molecules in which an ancillary ligand iscoordinated to a central transition metal atom. The ligand may becoordinated to the transition metal by covalent bond and/or electrondonation coordination or intermediate bonds. The transition metalcomplexes are generally subjected to activation to perform theirpolymerization or oligomerization function using an activator which isbelieved to create a cation as a result of the removal of an anionicgroup, often referred to as a leaving group, from the transition metal.

As used herein, the numbering scheme for the Periodic Table groups isthe new notation as set out in Chemical and Engineering News, 63(5), 27(1985).

For purposes of this invention and the claims thereto, Me is methyl, Etis ethyl, Bu is butyl, t-Bu and ^(t)Bu are tertiary butyl, Pr is propyl,iPr and ^(i)Pr are isopropyl, Cy is cyclohexyl, THF (also referred to asthe is tetrahydrofuran, Bn is benzyl, and Ph is phenyl.

Unless otherwise indicated, the term “substituted” means that a hydrogengroup has been replaced with a hydrocarbyl group, a heteroatom, or aheteroatom containing group. For example, methyl cyclopentadiene (Cp) isa Cp group substituted with a methyl group and ethyl alcohol is an ethylgroup substituted with an —OH group.

The terms “hydrocarbyl radical,” “hydrocarbyl,” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise, the terms“group,” “radical,” and “substituent” are also used interchangeably inthis document. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be a C₁-C₁₀₀ radical, that may be linear, branched, orcyclic, and when cyclic, aromatic or non-aromatic.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃,GeR*₃, SnR*₃, PbR*₃ and the like or where at least one non-hydrocarbonatom or group has been inserted within the hydrocarbyl radical, such as—O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—,—Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—, —Sn(R*)₂—, —Pb(R*)₂—and the like, where R* is independently a hydrocarbyl or halocarbylradical, and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g., F,Cl, Br, I) or halogen-containing group (e.g., CF₃).

Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂,SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at leastone non-carbon atom or group has been inserted within the halocarbylradical such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—,—As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—,—Sn(R*)₂—, —Pb(R*)₂— and the like, where R* is independently ahydrocarbyl or halocarbyl radical provided that at least one halogenatom remains on the original halocarbyl radical. Additionally, two ormore R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

Silylcarbyl radicals (also called silylcarbyls) are groups in which thesilyl functionality is bonded directly to the indicated atom or atoms.Examples include SiH₃, SiH₂R*, SiHR*₂, SiR*₃, SiH₂(OR*), SiH(OR*)₂,Si(OR*)₃, SiH₂(NR*₂), SiH(NR*₂)₂, Si(NR*₂)₃, and the like where R* isindependently a hydrocarbyl or halocarbyl radical and two or more R* mayjoin together to form a substituted or unsubstituted saturated,partially unsaturated or aromatic cyclic or polycyclic ring structure.Preferred silylcarbyls are of formula SiR*₃.

Polar radicals or polar groups (also referred to as functional groups)are groups in which the heteroatom functionality is bonded directly tothe indicated atom or atoms. They include heteroatoms of groups 13-17 ofthe periodic table either alone or connected to other elements bycovalent or other interactions such as ionic, van der Waals forces, orhydrogen bonding. Examples of functional groups include carboxylic acid,acid halide, carboxylic ester, carboxylic salt, carboxylic anhydride,aldehyde and their chalcogen (Group 14) analogues, alcohol and phenol,ether, peroxide and hydroperoxide, carboxylic amide, hydrazide andimide, amidine and other nitrogen analogues of amides, nitrile, amineand imine, azo, nitro, other nitrogen compounds, sulfur acids, seleniumacids, thiols, sulfides, sulfoxides, sulfones, phosphines, phosphates,other phosphorus compounds, silanes, boranes, borates, alanes,aluminates. Polar groups may also be taken broadly to include organicpolymer supports or inorganic support material such as alumina, andsilica. Preferred examples of polar groups include NR*₂, OR*, SeR*,TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SnR*₃, PbR*₃ and the like where R*is independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl orsubstituted halocarbyl radical as defined above and two R* may jointogether to form a substituted or unsubstituted saturated, partiallyunsaturated or aromatic cyclic or polycyclic ring structure.Particularly preferred examples of polar groups include NR*₂ and PR*₂.

The term “catalyst system” is defined to mean a complex/activator pair.When “catalyst system” is used to describe such a pair beforeactivation, it means the unactivated catalyst complex (precatalyst)together with an activator and, optionally, a co-activator. When it isused to describe such a pair after activation, it means the activatedcomplex and the activator or other charge-balancing moiety. Thetransition metal compound may be neutral as in a precatalyst, or acharged species with a counter ion as in an activated catalyst system.

Complex, as used herein, is also often referred to as catalystprecursor, precatalyst, catalyst, catalyst compound, transition metalcompound, or transition metal complex. These words are usedinterchangeably. Activator and cocatalyst are also used interchangeably.

A scavenger is a compound that is typically added to facilitatepolymerization by scavenging impurities. Some scavengers may also act asactivators and may be referred to as co-activators. A co-activator, thatis not a scavenger, may also be used in conjunction with an activator inorder to form an active catalyst. In some embodiments, a co-activatorcan be pre-mixed with the transition metal compound to form an alkylatedtransition metal compound.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, the olefin present in such polymer or copolymer is thepolymerized form of the olefin. For example, when a copolymer is said tohave an “ethylene” content of 35 wt % to 55 wt %, it is understood thatthe mer unit in the copolymer is derived from ethylene in thepolymerization reaction and said derived units are present at 35 wt % to55 wt %, based upon the weight of the copolymer. A “polymer” has two ormore of the same or different mer units. A “homopolymer” is a polymerhaving mer units that are the same. A “copolymer” is a polymer havingtwo or more mer units that are different from each other. A “terpolymer”is a polymer having three mer units that are different from each other.“Different” as used to refer to mer units indicates that the mer unitsdiffer from each other by at least one atom or are differentisomerically. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. An “ethylene polymer” or “ethylenecopolymer” is a polymer or copolymer comprising at least 50 mole %ethylene derived units, a “propylene polymer” or “propylene copolymer”is a polymer or copolymer comprising at least 50 mole % propylenederived units, and so on.

For the purposes of this invention, ethylene shall be considered anα-olefin.

As used herein, Mn is number average molecular weight, Mw is weightaverage molecular weight, and Mz is z average molecular weight, wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD), also referred to as polydispersity index (PDI), is defined to beMw divided by Mn. Unless otherwise noted, all molecular weight units(e.g., Mw, Mn, Mz) are g/mol.

Unless otherwise noted all melting points (T_(m)) are DSC second melt.

A “ring carbon atom” is a carbon atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring carbon atomsand para-methylstyrene also has six ring carbon atoms.

The term “aryl” or “aryl group” means a six carbon aromatic ring and thesubstituted variants thereof, including but not limited to, phenyl,2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means anaryl group where a ring carbon atom (or two or three ring carbon atoms)has been replaced with a heteroatom, preferably N, O, or S.

The term “ring atom” means an atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring atoms andtetrahydrofuran has 5 ring atoms.

The terms heteroaryl, heterocycle, heterocyclic ring, and heterocyclicligand are used interchangeably throughout this document.

A heterocyclic ring is a ring having a heteroatom in the ring structureas opposed to a heteroatom substituted ring where a hydrogen on a ringatom is replaced with a heteroatom. For example, tetrahydrofuran is aheterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatomsubstituted ring. A heterocyclic ring may be saturated, aromatic,pseudoaromatic, partially unsaturated or fully unsaturated. Asubstituted heterocycle is a heterocyclic ring that has had a hydrogengroup on the ring atoms replaced with a hydrocarbyl, a heteroatom, apolar group or a substituted hydrocarbyl.

As used herein the term “aromatic” also refers to pseudoaromaticheterocycles which are heterocyclic substituents that have similarproperties and structures (nearly planar) to aromatic heterocyclicligands, but are not by definition aromatic; likewise, the term aromaticalso refers to substituted aromatics.

The terms carbocycle, carbocyclic ring and carbocyclic ligand are usedinterchangeably throughout this document. A carbocycle is a ring ofcarbon atoms that may be saturated, unsaturated, or aromatic.Carbocycles may be fused together to form carbocycles containingmultiple rings, such as indane, naphthalene or anthracene. A substitutedcarbocycle is a ring of carbon atoms that has had a hydrogen group onthe ring atoms replaced with a hydrocarbyl, a heteroatom, a polar groupor a substituted hydrocarbyl.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn.

A solution polymerization means a polymerization process in which thepolymer is dissolved in a liquid polymerization medium, such as an inertsolvent or monomer(s) or their blends. A solution polymerization istypically homogeneous. A homogeneous polymerization is one where thepolymer product is dissolved in the polymerization medium. Such systemsare preferably not turbid as described in J. Vladimir Oliveira, C.Dariva and J. C. Pinto, Ind. Eng, Chem. Res. 29, 2000, 4627.

A bulk polymerization means a polymerization process in which themonomers and/or comonomers being polymerized are used as a solvent ordiluent using little or no inert solvent as a solvent or diluent. Asmall faction of inert solvent might be used as a carrier for catalystand scavenger. A bulk polymerization system contains less than 25 wt %of inert solvent or diluent, preferably less than 10 wt %, preferablyless than 1 wt %, preferably 0 wt %.

Unless otherwise stated, “catalyst activity” is a measure of how manygrams of polymer (P) are produced using a polymerization catalystcomprising W mmol of transition metal, over a period of time of T hours;and may be expressed by the following formula: P/(T×W).

Room temperature is 23° C. unless otherwise noted.

Catalyst Complexes

In a first aspect of the invention there is provided a heterocyclicamido transition metal complex (optionally for use in alkenepolymerization) represented by the formula (A), (B), (C), or (D):

-   wherein:-   M is a Group 3, 4, or 5 metal;-   Q¹ is a group that links R² and R³ by a three atom bridge    represented by the formula:-   -G¹-G²-G³- where G² is a group 15 or 16 atom that forms a dative    bond to M, G¹, and G³ are each a group 14 atom that are joined    together by two or three additional group 14, 15, or 16 atoms to    form a heterocycle or substituted heterocycle;-   Q² is a group that forms an anionic bond with M, said Q² group being    selected from O, S, CH₂, CHR¹⁷, C(R¹⁷)₂, NR¹⁷, or PR¹⁷, where each    R¹⁷ is independently selected from hydrogen, halogen, hydrocarbyls,    substituted hydrocarbyls, halocarbyls, substituted halocarbyls,    silylcarbyls, and polar groups;-   Q²′ is a group that forms an anionic bond with M, said Q²′ group    being selected from N, P, CH, or CR¹⁷ where R¹⁷ is defined as above;-   Q³ is -(T-T)- or -(T-T-T)-, where each T is a substituted or    unsubstituted group 14, 15, or 16 element so that together with the    “—C—N═C—” fragment it forms a 5- or 6-membered heterocycle or    substituted heterocycle;-   R¹ is selected from hydrocarbyls, substituted hydrocarbyls,    halocarbyls, substituted halocarbyls, and silylcarbyls;-   R² is -E(R¹²)(R¹³)— where E is carbon, silicon, or germanium, and    each R¹² and R¹³ is independently selected from the group consisting    of hydrogen, halogen, hydrocarbyls, substituted hydrocarbyls,    halocarbyls, substituted halocarbyls, silylcarbyls, and polar    groups;-   R³ is either C or N, and R⁴ and R⁵ are C, and R³ and R⁴ are part of    a five or six-membered carbocyclic or heterocyclic ring, which may    be substituted or unsubstituted, and R⁴ and R⁵ are part of a five or    six-membered carbocyclic or heterocyclic ring, which may be    substituted or unsubstituted;-   each J is independently selected from C, CH, CH₂, CR¹⁸, CHR¹⁸,    C(R¹⁸)₂, Si(R¹⁸)₂, SiH(R¹⁸), NH, NR¹⁸, O, or S, where R¹⁸ is    selected from hydrocarbyls, substituted hydrocarbyls, halocarbyls,    substituted halocarbyls, halogen, and silylcarbyls;-   each x is independently 3 or 4 representing the number of J groups    linked together in series;-   Y is selected from substituted and unsubstituted group 14 elements    including, but not limited to CH₂, CH(R¹⁸), C(R¹⁸)₂, C(O), and    C(NR¹⁸), where R¹⁸ is defined as above, and wherein the heteroatom    (such as O or N) may be datively bonded to M;-   Y′ is selected from substituted and unsubstituted group 14 elements    including, but not limited to CH, C(R¹⁸), where R¹⁸ is defined as    above;-   L is an anionic leaving group, where the L groups may be the same or    different and any two L groups may be linked to form a dianionic    leaving group;-   L′ is neutral Lewis base;-   n is 1, 2, or 3;-   w is 0, 1, 2, or 3;-   wherein n+w is no greater than 4; and-   wherein the tridentate dianionic ligand is chelated to the metal M    in such a fashion that the complex features an eight-membered ring    and a five-membered ring, which are indicated in the formulas (A)    through (D) by the numbers 8 and 5, respectively.

In another aspect of the invention there is provided a heterocyclicamido transition metal complex (optionally for use in alkenepolymerization) represented by the formula (E), (F), (G), (H), (I), or(J).

-   wherein:-   M, R¹, R², L, L′, n, w, Y, Y′, Q², and Q²′ are defined as above; E²    and E³ are independently selected from O, S, NH, or NR⁹, where R⁹ is    a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted    halocarbyl, halogen, silylcarbyl, or polar group;-   each R⁷ is independently selected from hydrogen, halogen,    hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted    halocarbyl, silylcarbyl, and polar groups, preferably hydroc arbyls;-   each R⁸ is independently selected from hydrogen, halogen,    hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted    halocarbyl, silylcarbyl, and polar groups, preferably hydrogen.

In any embodiment of the invention described herein, M may be Ti, Hf orZr, preferably Hf or Zr.

In any embodiment of the invention described herein, Q¹ may be asubstituted or unsubstituted imidazole, oxazole, or thiazole grouplinked to R³ and R² through the carbons in the 2 and 4 positions of theheterocyclic ring with the G² group being the atom in the 3 position,using the numbering schemes shown below for imidazole, oxazole, andthiazole.

In any embodiment of the invention described herein, G¹ and G³ are eacha group 14 atom that are joined together by two or three additionalgroup 14, 15, or 16 atoms to form a heterocycle or substitutedheterocycle.

In a preferred embodiment, Q² is CHR¹⁷, CH₂, or C(R¹⁷)₂ where R¹⁷ isselected from hydrocarbyls (such as alkyls and aryls), substitutedhydrocarbyls (such as heteroaryls), and silylcarbyl groups, preferablyR¹⁷ is a phenyl group or a substituted phenyl group optionallysubstituted with between one to five substituents that include F, Cl,Br, I, CF₃, NO₂, alkoxy, dialkylamino, aryl, and alkyl groups having 1to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, and isomers thereof.

In a preferred embodiment, Q² is NR¹⁷, where R¹⁷ is selected fromhydrocarbyls (such as alkyls and aryls), substituted hydrocarbyls (suchas heteroaryls), and silylcarbyl groups, preferably R¹⁷ is a phenylgroup or a substituted phenyl group optionally substituted with betweenone to five substituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy,dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, and isomers thereof.

In a preferred embodiment, Q² is O.

In a preferred embodiment, Q²′ is N.

In a preferred embodiment, M is Zr or Hf, n is 2, and w is 0.

In a preferred embodiment, Q²′ is CH or CR¹⁷ where R¹⁷ is selected fromhydrocarbyls (such as alkyls and aryls), substituted hydrocarbyls (suchas heteroaryls), and silylcarbyl groups, preferably R¹⁷ is a phenylgroup or a substituted phenyl group optionally substituted with betweenone to five substituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy,dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, and isomers thereof.

In any embodiment of the invention described herein, each T may beindependently selected from CH, C(hydrocarbyl), O, S, NH,N(hydrocarbyl), NMe, and NEt, where hydrocarbyl is preferably a C₁ toC₄₀ alkyl group, such as such as methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, or an isomer thereof.

In any embodiment of the invention described herein, E may be C, Si, orGe.

In any embodiment of the invention described herein, Y may be CH₂,CH(Ph), CH(Me), CH(t-Bu), CH(i-Pr), C(O), C(N-iPr), C(Me), C(NEt),C(N-t-Bu), or C(NPh).

In any embodiment of the invention described herein, Y′ may be CH,C(Ph), C(Me), C(t-Bu), C(Et), C(Pr), C(Bu), C(hexyl), or C(i-Pr).

In any embodiment of the invention described herein, Q² may be O, N(Ph),N(Mesityl), N(2,6-dimethylphenyl), N(2,6-diethylphenyl),N(2-methylphenyl), N(2-ethylphenyl), N(butyl), N(propyl), N(isopropyl),N(cyclohexyl), N(t-butyl), or N(2,6-diisopropylphenyl).

In any embodiment of the invention described herein, Q² may be CH₂,CHMe, CHEt, CHBu, CH(pentyl), CH(hexyl), CH(hexyl), CH(octyl),CH(nonyl), CH(decyl), or CHPh, O, N(Ph), N(Mesityl),N(2,6-dimethylphenyl), N(2,6-diethylphenyl), N(2-methylphenyl),N(2-ethylphenyl), N(butyl), N(propyl), N(isopropyl), N(cyclohexyl),N(t-butyl), or N(2,6-diisopropylphenyl).

In any embodiment of the invention described herein, Q²′ may be N, P,CH, C(Ph), C(Me), C(t-Bu), or C(i-Pr).

In any embodiment of the invention described herein, preferably L isselected from halide, alkyl, aryl, alkoxy, amido, hydrido, phenoxy,hydroxy, silyl, allyl, alkenyl, alkylsulfonate, alkylcarboxylate,arylcarboxylate, and alkynyl, preferably benzyl, methyl,trimethylsilylmethyl, dimethylamide, diethylamide, fluoride, andchloride. The selection of the leaving groups depends on the synthesisroute adopted for arriving at the complex and may be changed byadditional reactions to suit the later activation method inpolymerization. For example, a preferred L is alkyl when usingnon-coordinating anion activators such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)-borate or tris(pentafluorophenyl)borane. Inanother embodiment, two L groups may be linked to form a dianionicleaving group, for example oxalate.

In any embodiment of the invention described herein, preferably L′ isselected from ethers, thio-ethers, amines, nitriles, imines, pyridines,and phosphines, preferably ethers, preferably diethylether,dimethylsulfide, tetrahydrofuran and tetrahydrothiophene.

In any embodiment of the invention described herein, n is 1, 2, or 3 andw is 0, 1, 2, or 3, where n+w is no greater than 4, preferably n is 1 or2 and w is 0 or 1, and n+w is 2. Alternately, n is 2, w is 0, and n+w is2.

In any embodiment of the invention described herein, R¹ may be selectedfrom the group consisting of alkyl, aryl, heteroaryl, and silyl groups,preferably R¹ is selected from phenyl groups that are variouslysubstituted with between zero to five substituents that include F, Cl,Br, I, CF₃, NO₂, alkoxy, dialkylamino, aryl, and alkyl groups having 1to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, and isomers thereof. Some specific exampleswould include R¹ being chosen from a group including 2-methylphenyl,2-isopropylphenyl, 2-ethylphenyl, 2,6-dimethylphenyl, mesityl,2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl,2-methyl-6-isopropylphenyl, and 2-ethyl-6-methylphenyl.

In any embodiment of the invention described herein, R² may be selectedfrom moieties where E is carbon, especially a moiety —C(R¹²)(R¹³)— whereR¹² is hydrogen and R¹³ is an aryl group or a benzyl group (preferably aphenyl ring linked through an alkylene moiety such as methylene to the Catom). The phenyl group may then be substituted as discussed above forR¹. Useful R² groups include CH₂, CMe₂, SiMe₂, SiEt₂, SiPr₂, SiBu₂,SiPh₂, Si(aryl)₂, Si(alkyl)₂, CH(aryl), CH(Ph), CH(alkyl), CH(mesityl),and CH(2-isopropylphenyl). Particularly useful R² groups include CH₂,CMe₂, SiMe₂, SiEt₂, SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂, and Si(alkyl)₂,CH(aryl), CH(Ph), CH(alkyl), CH(mesityl), and CH(2-isopropylphenyl),where alkyl is a C₁ to C₄₀ alkyl group, aryl is a C₅ to C₄₀ aryl group.

In some embodiments of the invention, R² is preferably CH(mesityl).

In any embodiment of the invention described herein, R² is representedby the formula:

where R¹² is hydrogen, alkyl, aryl, or halogen; and R¹³ is hydrogen,alkyl, aryl, or halogen.

In any embodiment of the invention described herein, R¹² and R¹³ may be,independently, hydrogen, a C₁ to C₂₀ alkyl, preferably methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, or an isomer thereof), or a C₅ to C₄₀ aryl group (preferably aC₆ to C₂₀ aryl group, preferably phenyl or substituted phenyl or anisomer thereof, preferably phenyl, 2-isopropylphenyl, or2-tertbutylphenyl).

In any embodiment of the invention described herein, R³ may be C or N.

In any embodiment of the invention described herein, R⁴ and R⁵ are C.

In any embodiment of the invention described herein, each J may beindependently selected from C, CH, CH₂, Si(R¹⁸)₂, SiH(R¹⁸), NR¹⁸, O, orS, where R¹⁸ is selected from hydrocarbyls, substituted hydrocarbyls,and silylcarbyls.

In any embodiment of the invention described herein, each x may be 3 or4.

In any embodiment of the invention described herein, R¹ and R¹⁷ eachcontain from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms.

In any embodiment of the invention described herein, M may be Ti, Zr, orHf, and E is carbon, with Zr or Hf based complexes being especiallypreferred.

In an alternate embodiment of the invention described herein, E iscarbon and R¹ is selected from phenyl groups that are substituted with0, 1, 2, 3, 4, or 5 substituents selected from the group consisting ofF, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino, hydrocarbyl, andsubstituted hydrocarbyls groups with from one to ten carbons.

In a preferred embodiment, Q²′ is nitrogen and Y′ is CH orC(hydrocarbyl), where the hydrocarbyl group contains 1 to 20 carbonatoms.

In a preferred embodiment, Q²′ and Y′ are each independently CH orC(hydrocarbyl), where each hydrocarbyl group contains 1 to 20 carbonatoms.

In a preferred embodiment, Q² is N(hydrocarbyl) and Y is CH₂ orCH(hydrocarbyl), where the hydrocarbyl groups are independently selectedfrom groups that contain 1 to 20 carbon atoms.

In a preferred embodiment, Q² and Y are each independently CH₂ orCH(hydrocarbyl), where each hydrocarbyl groups contains 1 to 20 carbonatoms.

In a preferred embodiment, Y is selected from CH₂ or CH(hydrocarbyl),and Q² is not CH₂, CH(hydrocarbyl), or C(hydrocarbyl)₂, where thehydrocarbyl groups are independently selected from groups that contain 1to 20 carbon atoms.

In a preferred embodiment, Q² is not CH₂, CH(hydrocarbyl), orC(hydrocarbyl)₂, where the hydrocarbyl groups are independently selectedfrom groups that contain 1 to 20 carbon atoms.

In a preferred embodiment, M is zirconium, n is 2, w is 0, and R¹ is a2,6-dialkylphenyl group containing between 8 and 20 carbons.

In a preferred embodiment, M is hafnium, n is 2, w is 0, and R¹ is a2,6-dialkylphenyl group containing between 8 and 20 carbons.

In a preferred embodiment, M is zirconium, L is a hydrocarbyl groupcontaining 1 to 6 carbons, n is 2, w is 0, and R¹ is a 2,6-dialkylphenylgroup containing between 8 and 20 carbons.

In a preferred embodiment, M is hafnium, L is a hydrocarbyl groupcontaining 1 to 6 carbons, n is 2, w is 0, and R¹ is a 2,6-dialkylphenylgroup containing between 8 and 20 carbons.

In a preferred embodiment, M is zirconium, L is a hydrocarbyl groupcontaining 1 to 6 carbons, n is 2, w is 0, and Q²′ is nitrogen.

In a preferred embodiment, M is hafnium, L is a hydrocarbyl groupcontaining 1 to 6 carbons, n is 2, w is 0, and Q²′ is nitrogen.

Preferred pairing of R² and Y groups (expressed as R² & Y) includes:(CH₂ & CH(Ph)), (CMe₂ & CH(Ph)), (CH₂ & CH(aryl)), (CH₂ & CH(alkyl)),(CH(aryl) & CH(aryl)), (CH(aryl) & CH(alkyl)), (CH(mesityl) & CH(aryl)),and (CH(mesityl) & CH(alkyl)) where alkyl is a C₁ to C₄₀ alkyl group(preferably C₁ to C₂₀ alkyl, preferably one or more of methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, and isomers thereof), aryl is a C₅ to C₄₀ aryl group(preferably a C₆ to C₂₀ aryl group, preferably phenyl or substitutedphenyl, preferably phenyl, 2-isopropylphenyl, or 2-tertbutylphenyl).

Preferred pairing of R¹ and R² groups (expressed as R¹ & R²) includes:(2,6-diisopropylphenyl & CH₂), (2,6-diisopropylphenyl & CH(mesityl)),(2,6-diisopropylphenyl & CHPh), (2,6-diisopropylphenyl & CH(aryl)),(2,6-disubstitutedphenyl & CH(aryl)), where alkyl is a C₁ to C₄₀ alkylgroup (preferably C₁ to C₂₀ alkyl, preferably one or more of methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, and isomers thereof), aryl is a C₅ to C₄₀ aryl group(preferably a C₆ to C₂₀ aryl group, preferably phenyl or substitutedphenyl, preferably phenyl, 2-isopropylphenyl, or 2-tertbutylphenyl).

Preferred pairing of R¹ and Q² groups (expressed as R¹ & Q²) includes:(2,6-di(alkyl)phenyl & N(alkyl)), where alkyl is a C₁ to C₄₀ alkyl group(preferably C₁ to C₂₀ alkyl, preferably one or more of methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, and isomers thereof), aryl is a C₅ to C₄₀ aryl group(preferably a C₆ to C₂₀ aryl group, preferably phenyl or substitutedphenyl, preferably phenyl, 2-isopropylphenyl, or 2-tertbutylphenyl).

Preferred pairing of R¹ and Q² groups (expressed as R¹ & Q²) includes:(2,6-diisopropylphenyl & CH₂), (2,6-diisopropylphenyl & CH(alkyl)),(2,6-diisopropylphenyl & CHPh), (2,6-di(alkyl)phenyl & N(alkyl)), wherealkyl is a C₁ to C₄₀ alkyl group (preferably C₁ to C₂₀ alkyl, preferablyone or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is aC₅ to C₄₀ aryl group (preferably a C₆ to C₂₀ aryl group, preferablyphenyl or substituted phenyl, preferably phenyl, 2-isopropylphenyl, or2-tertbutylphenyl).

In another embodiment, R² is CH₂ or CMe₂ and Y is selected from thegroup consisting of CH(Ph), CH(aryl), CH(mesityl), and CH(alkyl), wherealkyl is a C₁ to C₄₀ alkyl group (preferably C₁ to C₂₀ alkyl, preferablyone or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is aC₅ to C₄₀ aryl group (preferably a C₆ to C₂₀ aryl group, preferablyphenyl or substituted phenyl, preferably phenyl, 2-isopropylphenyl, or2-tertbutylphenyl).

In any embodiment described herein, E is preferably carbon.

In a preferred embodiment, the heterocyclic amido transition metalcomplex is represented by the Formula (A), (B), (C), or (D) above, and Mis a Group 4 metal preferably Zr or Hf, preferably Hf.

In a preferred embodiment, the heterocyclic amido transition metalcomplex is represented by the Formula (A), (B), (C) or (D) above, and inthe R² group R¹² is H and R¹³ is a group containing between 1 to 100(preferably 6 to 40, preferably 6 to 30) carbons, M is a Group 4 metal(preferably Zr or Hf, preferably Hf), E is carbon, alternately in the R²group R¹² is the same as R¹³ and is preferably hydrogen or methyl.

In a preferred embodiment, the heterocyclic amido transition metalcomplex is represented by the Formula (A), (B), (C) or (D) above, andboth R¹² and R¹³ in the R² group are a C₁ to C₁₀₀ alkyl group(preferably a C₆ to C₄₀ alkyl group, preferably C₆ to C₃₀ alkyl group,alternately a C₁ to C₁₂ alkyl group, alternately a C₁ to C₆ alkyl group,alternately methyl, ethyl, propyl, butyl, pentyl hexyl, octyl, nonyl,decyl, or an isomer thereof).

In another aspect of the invention there are provided various processesfor synthesizing the complexes described herein.

Synthesis Methods

The complexes described herein may be prepared by reaction of moleculescontaining a reactive double or triple bond (shown as XY in the drawingsbelow) with an appropriate transition metal complex (shown asintermediate A in the drawings below). Transition metal complexes usefulfor this process may be neutral or cationic and will have a metal-carbonbond that reacts with the double or triple bond of an unsaturatedreactant to form the inventive complex via the formal insertion of theXY bond into the aforementioned metal-carbon bond. The product of suchan insertion reaction will feature a new covalent bond between thetransition metal center and at least one of the atoms of the XY group.Such reactions may be used to prepare the inventive complexes forisolation purposes. Alternatively, these reactions may be used togenerate the inventive complexes in situ, which may be desirable forapplication in an olefin polymerization process. General examples of theinsertion reaction are shown in the two equations below.

Insertion reaction involving XY molecule containing a reactive triplebond:

Insertion reaction involving XY molecule containing a reactive doublebond:

In a useful embodiment the reactive XY molecule has a reactive CO doublebond. Molecules of this type that may be suitable for this applicationinclude, but are not limited to, ketones, aldehydes, isocyanates,amides, formamides, esters, and carbon dioxide. When X is oxygen, theinsertion products formed will typically have a new transitionmetal-oxygen bond. The Y group is usefully selected from a list thatincludes, but is not limited to, CH₂, CH(alkyl), CH(aryl), C(alkyl)₂,C(aryl)₂, C(alkyl)(aryl), C═N(alkyl), C═N(aryl), C(NH)(alkyl),C(NH)(aryl), C(alkyl)(alkoxy), C(alkyl)(aryloxy), C(aryl)(alkoxy),C(aryl)(aryloxy), and CO.

In another embodiment, the reactive XY molecule has a reactive CN doublebond. Molecules of this type that may be suitable for this applicationinclude, but are not limited to, imines, formimines, and carbodiimides.The insertion products formed will typically have a new transitionmetal-nitrogen bond, so the X group is NH, N(alkyl), N(aryl), or anothertype of substituted nitrogen. The Y group is selected from a list thatincludes, but is not limited to, CH(alkyl), CH(aryl), CH₂, CN(alkyl),and CN(aryl).

In another embodiment, the reactive XY molecule has a reactive CN triplebond. Molecules of this type that may be suitable for this applicationinclude, but are not limited to, nitriles. The insertion products formedwill typically have a new transition metal-nitrogen bond, so the X groupis nitrogen. The Y group is selected from a list that includes, but isnot limited to, CH, C(alkyl), and C(aryl).

In another embodiment, the reactive XY molecule has a reactive CC doublebond. Molecules of this type that may be suitable for this applicationinclude, but are not limited to, ethylene, propylene, alpha olefins,internal olefins, allenes, diolefins, and styrene. The insertionproducts formed will typically have a new transition metal-carbon bond,so the X group is CH₂, CH(alkyl), CH(aryl), C(alkyl)₂, C(aryl)₂,C(alkyl)(aryl), or other disubstituted carbon, where alkyl is a C₁ toC₄₀ alkyl group (preferably C₁ to C₂₀ alkyl, preferably one or more ofmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, and isomers thereof), aryl is a C₅ to C₄₀ arylgroup (preferably a C₆ to C₂₀ aryl group, preferably phenyl orsubstituted phenyl). The Y group is selected from a list that includes,but is not limited to, CH₂, CH(alkyl), CH(aryl), C(alkyl)₂, C(aryl)₂,C(alkyl)(aryl), and other disubstituted carbons, where alkyl is a C₁ toC₄₀ alkyl group (preferably C₁ to C₂₀ alkyl, preferably one or more ofmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, and isomers thereof), aryl is a C₅ to C₄₀ arylgroup (preferably a C₆ to C₂₀ aryl group, preferably phenyl orsubstituted phenyl).

In another embodiment, the reactive XY molecule has a reactive CC triplebond. Molecules of this type that may be suitable for this applicationinclude, but are not limited to, acetylene, terminal alkynes, andinternal alkynes. The insertion products formed will typically have anew transition metal-carbon bond, so the X group is CH, C(alkyl), orC(aryl) where alkyl is a C₁ to C₄₀ alkyl group (preferably C₁ to C₂₀alkyl, preferably one or more of methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomersthereof), aryl is a C₅ to C₄₀ aryl group (preferably a C₆ to C₂₀ arylgroup, preferably phenyl or substituted phenyl). The Y group is selectedfrom a list that includes, but is not limited to, CH, C(alkyl), andC(aryl), where alkyl is a C₁ to C₄₀ alkyl group (preferably C₁ to C₂₀alkyl, preferably one or more of methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomersthereof), aryl is a C₅ to C₄₀ aryl group (preferably a C₆ to C₂₀ arylgroup, preferably phenyl or substituted phenyl).

In another embodiment, the inventive transition metal complex features acoordinated tridentate dianionic ligand that has a central neutraldative donor (N^(dative)) and a pair of anionic donor groups(N^(anionic) and X) joined to the central dative donor group. The tworings formed by the chelation of the [N^(anionic)-N^(dative)-X]tridentate ligand to the transition metal center, ignoring anyadditional bonding to the Y group, have sizes of 5 and 8 atoms. Theseare shown in the drawing below. The 8-membered chelate ring is comprisesthe transition metal M, X, Y, N^(dative), and the four additional atomsthat form the shortest linkage between N^(dative) and Y that excludes M.The 5-membered chelate ring comprises the transition metal M,N^(dative), N^(anionic), and two additional atoms that form the shortestlinkage between N^(dative) and N^(anionic) that excludes M.

In another embodiment the inventive transition metal complex features acoordinated tridentate dianionic ligand like the one drawn below. Ring-Arepresents a 5 or 6 membered heterocyclic ring that has a nitrogen atomcapable of forming a dative bond with the metal M. Examples of ring-Ainclude, but are not limited to, derivatives of imidazole,N-alkylimidazole, thiazole, and oxazole. Ring-B and ring-C are each a 5or 6-membered ring comprised of hydrogen, and group 14, 15, and/or 16elements. The two chelate rings formed by the coordination of the[N^(anionic)-N_(dative)-X] tridentate ligand to the transition metalcenter, ignoring any additional bonding to the Y group, have sizes of 5and 8 atoms. The 8-membered chelate ring comprises the transition metalM, X, Y, N^(dative) and the four additional atoms that form the shortestlinkage between N^(dative) and Y that excludes M. The 5-membered chelatering is comprised of the transition metal M, N^(dative), N^(anionic),andtwo additional atoms that form the shortest linkage between N^(dative)and N^(anionic) that excludes M.

In another embodiment, the inventive complex is prepared by a route thatdoes not involve the reaction of an intermediate transition metalcomplex (e.g., intermediate A) with a small molecule XY. Instead, theneutral multidentate ligand is pre-formed in a multistep organicsynthesis. Then this preformed ligand may be complexed to the transitionmetal using known methods. For example, the “free-base” form of themultidentate ligand may be deprotonated using two equivalents of astrong base (e.g., butyllithium) to form a lithium salt of the ligand(i.e., Li₂[ligand]). This lithium salt may then be reacted with atransition metal halides, such as HfCl₄, ZrCl₄, TiCl₄, or TiCl₃ to formthe desired complex (e.g., [ligand]HfCl₂, [ligand]ZrCl₂, [ligand]TiCl₂,or [ligand]TiCl) with the elimination of lithium chloride byproduct.Alternatively, the free-base ligand may be reacted with a basictransition metal reagent such as, Hf(CH₂Ph)₄, Hf(CH₂Ph)₂Cl₂(OEt₂),Zr(CH₂Ph)₄, Zr(CH₂Ph)₂Cl₂(OEt₂), Zr(NMe₂)₄, Hf(NEt₂)₄, orHf(NMe₂)₂Cl₂(1,2-dimethoxyethane), to form the desired complex (e.g.,[ligand]Hf(CH₂Ph)₂,[ligand]HfCl₂, [ligand]Zr(NMe₂)₂, [ligand]ZrCl₂) withthe elimination of byproduct conjugate acid from the acid-base reaction.

Activators

After the complexes have been synthesized, catalyst systems may beformed by combining them with activators in any manner known from theliterature, including by supporting them for use in slurry or gas phasepolymerization. The catalyst systems may also be added to or generatedin solution polymerization or bulk polymerization (in the monomer). Thecatalyst system typically comprises a complex as described above and anactivator such as alumoxane or a non-coordinating anion. Activation maybe performed using alumoxane solution including methyl alumoxane,referred to as MAO, as well as modified MAO, referred to herein as MMAO,containing some higher alkyl groups to improve the solubility.Particularly useful MAO can be purchased from Albemarle, typically in a10 wt % solution in toluene. The catalyst system employed in the presentinvention preferably uses an activator selected from alumoxanes, such asmethyl alumoxane, modified methyl alumoxane, ethyl alumoxane, iso-butylalumoxane, and the like.

When an alumoxane or modified alumoxane is used, thecomplex-to-activator molar ratio is from about 1:3000 to 10:1;alternatively 1:2000 to 10:1; alternatively 1:1000 to 10:1;alternatively 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1;alternatively 1:10 to 1:1. When the activator is an alumoxane (modifiedor unmodified), some embodiments select the maximum amount of activatorat a 5000-fold molar excess over the catalyst precursor (per metalcatalytic site). The preferred minimum activator-to-complex ratio is 1:1molar ratio.

Activation may also be performed using non-coordinating anions, referredto as NCA's, of the type described in EP 277 003 A1 and EP 277 004 A1.NCA may be added in the form of an ion pair using, for example,[DMAH]+[NCA]− in which the N,N-dimethylanilinium (DMAH) cation reactswith a basic leaving group on the transition metal complex to form atransition metal complex cation and [NCA]−. The cation in the precursormay, alternatively, be trityl. Alternatively, the transition metalcomplex may be reacted with a neutral NCA precursor, such as B(C₆F₅)₃,which abstracts an anionic group from the complex to form an activatedspecies. Useful activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (i.e., [PhNMe₂H]B(C₆F₅)₄) andN,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph isphenyl, and Me is methyl.

Additionally, preferred activators useful herein include those describedin U.S. Pat. No. 7,247,687 at column 169, line 50 to column 174, line43, particularly column 172, line 24 to column 173, line 53.

Non-coordinating anion (NCA) is defined to mean an anion either thatdoes not coordinate to the catalyst metal cation or that does coordinateto the metal cation, but only weakly. The term NCA is also defined toinclude multicomponent NCA-containing activators, such asN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain anacidic cationic group and the non-coordinating anion. The term NCA isalso defined to include neutral Lewis acids, such astris(pentafluorophenyl)boron, that can react with a catalyst to form anactivated species by abstraction of an anionic group. An NCA coordinatesweakly enough that a neutral Lewis base, such as an olefinically oracetylenically unsaturated monomer can displace it from the catalystcenter. Any metal or metalloid that can form a compatible, weaklycoordinating complex may be used or contained in the noncoordinatinganion. Suitable metals include, but are not limited to, aluminum, gold,and platinum. Suitable metalloids include, but are not limited to,boron, aluminum, phosphorus, and silicon. A stoichiometric activator canbe either neutral or ionic. The terms ionic activator, andstoichiometric ionic activator can be used interchangeably. Likewise,the terms neutral stoichiometric activator, and Lewis acid activator canbe used interchangeably. The term non-coordinating anion includesneutral stoichiometric activators, ionic stoichiometric activators,ionic activators, and Lewis acid activators.

In an embodiment of the invention described herein, the non-coordinatinganion activator is represented by the following formula (1):

(Z)_(d) ⁺(A^(d−))   (1)

wherein Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base;H is hydrogen and (L-H)⁺ is a Bronsted acid; Ad^(d−) is anon-coordinating anion having the charge d−; and d is an integer from 1to 3.

When Z is (L-H) such that the cation component is (L-H)d+, the cationcomponent may include Bronsted acids such as protonated Lewis basescapable of protonating a moiety, such as an alkyl or aryl, from thecatalyst precursor, resulting in a cationic transition metal species, orthe activating cation (L-H)d+ is a Bronsted acid, capable of donating aproton to the catalyst precursor resulting in a transition metal cation,including ammoniums, oxoniums, phosphoniums, silyliums, and mixturesthereof, or ammoniums of methylamine, aniline, dimethylamine,diethylamine, N-methylaniline, diphenylamine, trimethylamine,triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine,p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniumsfrom triethylphosphine, triphenylphosphine, and diphenylphosphine,oxoniums from ethers, such as dimethyl ether diethyl ether,tetrahydrofuran, and dioxane, sulfoniums from thioethers, such asdiethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid, it may be represented by the formula:(Ar₃C+), where Ar is aryl or aryl substituted with a heteroatom, or a C₁to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented by theformula: (Ph₃C+), where Ph is phenyl or phenyl substituted with aheteroatom, and/or a C1 to C40 hydrocarbyl. In an embodiment, thereducible Lewis acid is triphenyl carbenium.

Embodiments of the anion component Ad− include those having the formula[Mk+Qn]d+ wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5 or 6, or 3, 4, 5or 6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, or boron or aluminum, and Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl radicals, said Q having up to 20 carbon atoms with theproviso that in not more than one occurrence is Q a halide, and two Qgroups may form a ring structure. Each Q may be a fluorinatedhydrocarbyl radical having 1 to 20 carbon atoms, or each Q is afluorinated aryl radical, or each Q is a pentafluoryl aryl radical.Examples of suitable Ad− components also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

In an embodiment in any of the NCA's represented by Formula 1 describedabove, the anion component Ad− is represented by the formula[M*k*+Q*n*]d*− wherein k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5, or 6 (or1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* is independently selectedfrom hydride, bridged or unbridged dialkylamido, halogen, alkoxide,aryloxide, hydrocarbyl radicals, said Q* having up to 20 carbon atomswith the proviso that in not more than 1 occurrence is Q* a halogen.

This invention also relates to a method to polymerize olefins comprisingcontacting olefins (such as propylene) with a catalyst complex asdescribed above and an NCA activator represented by the Formula (2):

R_(n)M**(ArNHal)_(4−n)   (2)

where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 2also comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, or the cation is Z_(d)+as described above.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, R is selected from the group consisting of C₁to C₃₀ hydrocarbyl radicals. In an embodiment, C₁ to C₃₀ hydrocarbylradicals may be substituted with one or more C₁ to C₂₀ hydrocarbylradicals, halide, hydrocarbyl substituted organometalloid, dialkylamido,alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,arylphosphide, or other anionic substituent; fluoride; bulky alkoxides,where bulky means C₄ to C₂₀ hydrocarbyl radicals; —SRa, —NRa₂, and—PRa₂, where each R^(a) is independently a monovalent C₄ to C₂₀hydrocarbyl radical comprising a molecular volume greater than or equalto the molecular volume of an isopropyl substitution or a C₄ to C₂₀hydrocarbyl substituted organometalloid having a molecular volumegreater than or equal to the molecular volume of an isopropylsubstitution.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, the NCA also comprises cation comprising areducible Lewis acid represented by the formula: (Ar₃C+), where Ar isaryl or aryl substituted with a heteroatom, and/or a C₁ to C₄₀hydrocarbyl, or the reducible Lewis acid represented by the formula:(Ph3C+), where Ph is phenyl or phenyl substituted with one or moreheteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, the NCA may also comprise a cationrepresented by the formula, (L-H)d+, wherein L is an neutral Lewis base;H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or (L-H)d+is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums,silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. No. 7,297,653 and U.S. Pat. No. 7,799,879, which are fullyincorporated by reference herein.

In an embodiment, an activator useful herein comprises a salt of acationic oxidizing agent and a non-coordinating, compatible anionrepresented by the Formula (3):

(OX^(e+))_(d) (A^(d−))_(e)   (3)

wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2 or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anionhaving the charge of d− (as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Suitable embodiments of A^(d−) includetetrakis(pentafluorophenyl)borate.

Activators useful in catalyst systems herein include: trimethylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, and the types disclosed in U.S. Pat.No. 7,297,653, which is fully incorporated by reference herein.

Suitable activators also include: N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph3C+][B(C6F5)4−], [Me3NH+][B(C6F5)4−];1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In an embodiment, the activator comprises a triaryl carbonium (such astriphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyeborate, triphenylcarbeniumtetrakis(perfluorobiphenyeborate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In an embodiment, two NCA activators may be used in the polymerizationand the molar ratio of the first NCA activator to the second NCAactivator can be any ratio. In an embodiment, the molar ratio of thefirst NCA activator to the second NCA activator is 0.01:1 to 10,000:1,or 0.1:1 to 1000:1, or 1:1 to 100:1.

In an embodiment of the invention, the NCA activator-to-catalyst ratiois a 1:1 molar ratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to500:1 or 1:1 to 1000:1. In an embodiment, the NCA activator-to-catalystratio is 0.5:1 to 10:1, or 1:1 to 5:1.

In an embodiment, the catalyst compounds can be combined withcombinations of alumoxanes and NCA's (see for example, U.S. Pat. No.5,153,157; U.S. Pat. No. 5,453,410; EP 0 573 120 B1; WO 94/07928; and WO95/14044 which discuss the use of an alumoxane in combination with anionizing activator, all of which are incorporated by reference herein).

In a preferred embodiment of the invention, when an NCA (such as anionic or neutral stoichiometric activator) is used, thecomplex-to-activator molar ratio is typically from 1:10 to 1:1; 1:10 to10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1;1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to3:1; 1:5 to 5:1; 1:1 to 1:1.2.

Alternately, a co-activator or chain transfer agent, such as a group 1,2, or 13 organometallic species (e.g., an alkyl aluminum compound suchas tri-n-octyl aluminum), may also be used in the catalyst systemherein. The complex-to-co-activator molar ratio is from 1:100 to 100:1;1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1;1:5 to 5:1; 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.

Chain Transfer Agents

A “chain transfer agent” is any agent capable of hydrocarbyl and/orpolymeryl group exchange between a coordinative polymerization catalystand the metal center of the chain transfer agent during a polymerizationprocess. The chain transfer agent can be any desirable chemical compoundsuch as those disclosed in WO 2007/130306. Preferably, the chaintransfer agent is selected from Group 2, 12 or Group 13 alkyl or arylcompounds; preferably zinc, magnesium or aluminum alkyls or aryls;preferably where the alkyl is a C₁ to C₃₀ alkyl, alternately a C₂ to C₂₀alkyl, alternately a C₃ to C₁₂ alkyl, typically selected independentlyfrom methyl, ethyl, propyl, butyl, isobutyl, tertbutyl, pentyl, hexyl,cyclohexyl, phenyl, octyl, nonyl, decyl, undecyl, and dodecyl; and wheredi-ethylzinc is particularly preferred.

In a particularly useful embodiment, this invention relates to acatalyst system comprising activator, catalyst complex as describedherein and chain transfer agent wherein the chain transfer agent isselected from Group 2, 12, or Group 13 alkyl or aryl compounds.

In a particularly useful embodiment, the chain transfer agent isselected from dialkyl zinc compounds, where the alkyl is selectedindependently from methyl, ethyl, propyl, butyl, isobutyl, tertbutyl,pentyl, hexyl, cyclohexyl, and phenyl.

In a particularly useful embodiment, the chain transfer agent isselected from trialkyl aluminum compounds, where the alkyl is selectedindependently from methyl, ethyl, propyl, butyl, isobutyl, tertbutyl,pentyl, hexyl, cyclohexyl, and phenyl.

Useful chain transfer agents are typically present at from 10 or 20 or50 or 100 equivalents to 600 or 700 or 800 or 1000 equivalents relativeto the catalyst component. Alternately the chain transfer agent (“CTA”)is preset at a catalyst complex-to-CTA molar ratio of from about 1:3000to 10:1; alternatively 1:2000 to 10:1; alternatively 1:1000 to 10:1;alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1;alternatively 1:10 to 1:1.

Useful chain transfer agents include diethylzinc, tri-n-octyl aluminum,trimethylaluminum, triethylaluminum, tri-isobutylaluminum,tri-n-hexylaluminum, diethyl aluminum chloride, dibutyl zinc,di-n-propylzinc, di-n-hexylzinc, di-n-pentylzinc, di-n-decylzinc,di-n-dodecylzinc, di-n-tetradecylzinc, di-n-hexadecylzinc,di-n-octadecylzinc, diphenylzinc, diisobutylaluminum hydride,diethylaluminum hydride, di-n-octylaluminum hydride, dibutylmagnesium,diethylmagnesium, dihexylmagnesium, and triethylboron.

Supports

In some embodiments, the complexes described herein may be supported(with or without an activator) by any method effective to support othercoordination catalyst systems, effective meaning that the catalyst soprepared can be used for oligomerizing or polymerizing olefin in aheterogeneous process. The catalyst precursor, activator, co-activatorif needed, suitable solvent, and support may be added in any order orsimultaneously. Typically, the complex and activator may be combined insolvent to form a solution. Then the support is added, and the mixtureis stirred for 1 minute to 10 hours. The total solution volume may begreater than the pore volume of the support, but some embodiments limitthe total solution volume below that needed to form a gel or slurry(about 90% to 400%, preferably about 100-200% of the pore volume). Afterstirring, the residual solvent is removed under vacuum, typically atambient temperature and over 10-16 hours. But greater or lesser timesand temperatures are possible.

The complex may also be supported absent the activator; in that case,the activator (and co-activator if needed) is added to a polymerizationprocess's liquid phase. Additionally, two or more different complexesmay be placed on the same support. Likewise, two or more activators oran activator and co-activator may be placed on the same support.

Suitable solid particle supports are typically comprised of polymeric orrefractory oxide materials, each being preferably porous. Preferably anysupport material that has an average particle size greater than 10_(I)nn is suitable for use in this invention. Various embodiments selecta porous support material, such as for example, talc, inorganic oxides,inorganic chlorides, for example, magnesium chloride and resinoussupport materials such as polystyrene polyolefin or polymeric compoundsor any other organic support material and the like. Some embodimentsselect inorganic oxide materials as the support material including Group−2, −3, −4, −5, −13, or −14 metal or metalloid oxides. Some embodimentsselect the catalyst support materials to include silica, alumina,silica-alumina, and their mixtures. Other inorganic oxides may serveeither alone or in combination with the silica, alumina, orsilica-alumina. These are magnesia, titania, zirconia, and the like.Lewis acidic materials such as montmorillonite and similar clays mayalso serve as a support. In this case, the support can optionally doubleas the activator component, however, an additional activator may also beused.

The support material may be pretreated by any number of methods. Forexample, inorganic oxides may be calcined, chemically treated withdehydroxylating agents such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordancewith the invention, see for example the descriptions in WO 95/15815 andU.S. Pat. No. 5,427,991. The methods disclosed may be used with thecatalyst complexes, activators or catalyst systems of this invention toadsorb or absorb them on the polymeric supports, particularly if made upof porous particles, or may be chemically bound through functionalgroups bound to or in the polymer chains.

Useful supports typically have a surface area of from 10-700 m²/g, apore volume of 0.1-4.0 cc/g and an average particle size of 10-500 μm.Some embodiments select a surface area of 50-500 m²/g, a pore volume of0.5-3.5 cc/g, or an average particle size of 20-200 μm. Otherembodiments select a surface area of 100-400 m²/g, a pore volume of0.8-3.0 cc/g, and an average particle size of 30-100 μm. Useful supportstypically have a pore size of 10-1000 Angstroms, alternatively 50-500Angstroms, or 75-350 Angstroms.

The catalyst complexes described herein are generally deposited on thesupport at a loading level of 10-100 micromoles of complex per gram ofsolid support; alternately 20-80 micromoles of complex per gram of solidsupport; or 40-60 micromoles of complex per gram of support. But greateror lesser values may be used provided that the total amount of solidcomplex does not exceed the support's pore volume.

Polymerization

Inventive catalyst complexes are useful in polymerizing unsaturatedmonomers conventionally known to undergo metallocene-catalyzedpolymerization such as solution, slurry, gas-phase, and high-pressurepolymerization. Typically one or more of the complexes described herein,one or more activators, and one or more monomers are contacted toproduce polymer. In certain embodiments, the complexes may be supportedand as such will be particularly useful in the known, fixed-bed,moving-bed, fluid-bed, slurry, solution, or bulk operating modesconducted in single, series, or parallel reactors.

One or more reactors in series or in parallel may be used in the presentinvention. The complexes, activator and when required, co-activator, maybe delivered as a solution or slurry, either separately to the reactor,activated in-line just prior to the reactor, or preactivated and pumpedas an activated solution or slurry to the reactor. Polymerizations arecarried out in either single reactor operation, in which monomer,comonomers, catalyst/activator/co-activator, optional scavenger, andoptional modifiers are added continuously to a single reactor or inseries reactor operation, in which the above components are added toeach of two or more reactors connected in series. The catalystcomponents can be added to the first reactor in the series. The catalystcomponent may also be added to both reactors, with one component beingadded to first reaction and another component to other reactors. In onepreferred embodiment, the complex is activated in the reactor in thepresence of olefin.

In a particularly preferred embodiment, the polymerization process is acontinuous process.

Polymerization processes used herein typically comprise contacting oneor more alkene monomers with the complexes (and, optionally, activator)described herein. For purpose of this invention alkenes are defined toinclude multi-alkenes (such as dialkenes) and alkenes having just onedouble bond. Polymerization may be homogeneous (solution or bulkpolymerization) or heterogeneous (slurry-in-liquid diluent, or gasphase-in-gaseous diluent). In the case of heterogeneous slurry or gasphase polymerization, the complex and activator may be supported. Silicais useful as a support herein. Chain transfer agents (such as hydrogen,or diethyl zinc) may be used in the practice of this invention.

The present polymerization processes may be conducted under conditionspreferably including a temperature of about 30° C. to about 200° C.,preferably from 60° C. to 195° C., preferably from 75° C. to 190° C. Theprocess may be conducted at a pressure of from 0.05 MPa to 1500 MPa. Ina preferred embodiment, the pressure is between 1.7 MPa and 30 MPa, orin another embodiment, especially under supercritical conditions, thepressure is between 15 MPa and 1500 MPa.

Monomers

Monomers useful herein include olefins having from 2 to 20 carbon atoms,alternately 2 to 12 carbon atoms (preferably ethylene, propylene,butylene, pentene, hexene, heptene, octene, nonene, decene, anddodecene) and optionally also polyenes (such as dienes). Particularlypreferred monomers include ethylene, and mixtures of C₂ to C₁₀ alphaolefins, such as ethylene-propylene, ethylene-hexene, ethylene-octene,propylene-hexene, and the like.

The complexes described herein are also particularly effective for thepolymerization of ethylene, either alone or in combination with at leastone other olefinically unsaturated monomer, such as a C₃ to C₂₀α-olefin, and particularly a C₃ to C₁₂ α-olefin. Likewise, the presentcomplexes are also particularly effective for the polymerization ofpropylene, either alone or in combination with at least one otherolefinic ally unsaturated monomer, such as ethylene or a C₄ to C₂₀α-olefin, and particularly a C₄ to C₂₀ α-olefin. Examples of preferredα-olefins include ethylene, propylene, butene-1, pentene-1, hexene-1,heptene-1, octene-1, nonene-1, decene-1, dodecene-1, 4-methylpentene-1,3-methylpentene-1,3,5,5-trimethylhexene-1, and 5-ethylnonene-1.

In some embodiments, the monomer mixture may also comprise one or moredienes at up to 10 wt %, such as from 0.00001 to 1.0 wt %, for examplefrom 0.002 to 0.5 wt %, such as from 0.003 to 0.2 wt %, based upon themonomer mixture. Non-limiting examples of useful dienes include,cyclopentadiene, norbornadiene, dicyclopentadiene,5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 1,4-hexadiene,1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene,1,7-octadiene, 7-methyl-1,7-octadiene, 1,9-decadiene, land9-methyl-1,9-decadiene.

Where olefins are used that give rise to short chain branching, such aspropylene, the catalyst systems may, under appropriate conditions,generate stereoregular polymers or polymers having stereoregularsequences in the polymer chains.

Scavengers

In some embodiments, when using the complexes described herein,particularly when they are immobilized on a support, the catalyst systemwill additionally comprise one or more scavenging compounds. Here, theterm scavenging compound means a compound that removes polar impuritiesfrom the reaction environment. These impurities adversely affectcatalyst activity and stability. Typically, the scavenging compound willbe an organometallic compound such as the Group-13 organometalliccompounds of U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,241,025;WO-A-91/09882; WO-A-94/03506; WO-A-93/14132; and that of WO 95/07941.Exemplary compounds include triethyl aluminum, triethyl borane,tri-iso-butyl aluminum, methyl alumoxane, iso-butyl alumoxane, andtri-n-octyl aluminum. Those scavenging compounds having bulky or C₆-C₂₀linear hydrocarbyl substituents connected to the metal or metalloidcenter usually minimize adverse interaction with the active catalyst.Examples include triethylaluminum, but more preferably, bulky compoundssuch as tri-iso-butyl aluminum, tri-iso-prenyl aluminum, and long-chainlinear alkyl-substituted aluminum compounds, such as tri-n-hexylaluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum. Whenalumoxane is used as the activator, any excess over that needed foractivation will scavenge impurities and additional scavenging compoundsmay be unnecessary. Alumoxanes also may be added in scavengingquantities with other activators, e.g., methylalumoxane,[Me₂HNPh]+[B(pfp)₄]⁻ or B(pfp)₃ (perfluorophenyl=pfp=C₆F₅).

In a preferred embodiment, two or more complexes are combined withdiethyl zinc in the same reactor with monomer. Alternately, one or morecomplexes is combined with another catalyst (such as a metallocene) anda chain transfer agent, such as diethyl zinc and or tri-n-octylaluminum, in the same reactor with monomer.

The chain transfer agent may be the same as or different from thescavenger.

Polymer Products

While the molecular weight of the polymers produced herein is influencedby reactor conditions including temperature, monomer concentration andpressure, the presence of chain terminating agents and the like, thehomopolymer and copolymer products produced by the present process mayhave an Mw of about 1,000 to about 2,000,000 g/mol, alternately of about30,000 to about 600,000 g/mol, or alternately of about 100,000 to about500,000 g/mol, as determined by GPC. Preferred polymers produced heremay be homopolymers or copolymers. In a preferred embodiment, thecomonomer(s) are present at up to 50 mol %, preferably from 0.01 to 40mol %, preferably 1 to 30 mol %, preferably from 5 to 20 mol %.

In some embodiments herein, a multimodal polyolefin composition isproduced, comprising a first polyolefin component and at least anotherpolyolefin component, different from the first polyolefin component bymolecular weight, preferably such that the GPC trace has more than onepeak or inflection point.

The term “multimodal,” when used to describe a polymer or polymercomposition, means “multimodal molecular weight distribution,” which isunderstood to mean that the Gel Permeation Chromatography (GPC) trace,plotted as Absorbance versus Retention Time (seconds), has more than onepeak or inflection points. An “inflection point” is that point where thesecond derivative of the curve changes in sign (e.g., from negative topositive or vice versa). For example, a polyolefin composition thatincludes a first lower molecular weight polymer component (such as apolymer having an Mw of 100,000 g/mol) and a second higher molecularweight polymer component (such as a polymer having an Mw of 300,000g/mol) is considered to be a “bimodal” polyolefin composition.Preferably, the Mw's of the polymer or polymer composition differ by atleast 10%, relative to each other, preferably by at least 20%,preferably at least 50%, preferably by at least 100%, preferably by aleast 200%. Likewise, in a preferred embodiment, the Mw's of the polymeror polymer composition differ by 10% to 10,000%, relative to each other,preferably by 20% to 1000%, preferably 50% to 500%, preferably by atleast 100% to 400%, preferably 200% to 300%.

Unless otherwise indicated, measurements of weight average molecularweight (Mw), number average molecular weight (Mn), and z averagemolecular weight (Mz) are determined by Gel Permeation Chromatography(GPC) as described in Macromolecules, 2001, Vol. 34, No. 19, pg. 6812,which is fully incorporated herein by reference, including that, a HighTemperature Size Exclusion Chromatograph (SEC, Waters Alliance 2000),equipped with a differential refractive index detector (DRI) equippedwith three Polymer Laboratories PLgel 10 mm Mixed-B columns is used. Theinstrument is operated with a flow rate of 1.0 cm3 /min, and aninjection volume of 300 μL. The various transfer lines, columns anddifferential refractometer (the DRI detector) are housed in an ovenmaintained at 145C. Polymer solutions are prepared by heating 0.75 to1.5 mg/mL of polymer in filtered 1,2,4-Trichlorobenzene (TCB) containing˜1000 ppm of butylated hydroxy toluene (BHT) at 160° C. for 2 hours withcontinuous agitation. A sample of the polymer containing solution isinjected into to the GPC and eluted using filtered1,2,4-trichlorobenzene (TCB) containing ˜1000 ppm of BHT. The separationefficiency of the column set is calibrated using a series of narrow MWDpolystyrene standards reflecting the expected Mw range of the samplebeing analyzed and the exclusion limits of the column set. Seventeenindividual polystyrene standards, obtained from Polymer Laboratories(Amherst, Mass.) and ranging from Peak Molecular Weight (Mp) ˜580 to10,000,000, were used to generate the calibration curve. The flow rateis calibrated for each run to give a common peak position for a flowrate marker (taken to be the positive inject peak) before determiningthe retention volume for each polystyrene standard. The flow marker peakposition is used to correct the flow rate when analyzing samples. Acalibration curve (log(Mp) vs. retention volume) is generated byrecording the retention volume at the peak in the DRI signal for each PSstandard, and fitting this data set to a 2nd-order polynomial. Theequivalent polyethylene molecular weights are determined by using theMark-Houwink coefficients shown in Table B.

TABLE B Mark-Houwink coefficients Material K (dL/g) α PS 1.75 × 10⁻⁴0.67 PE 5.79 × 10⁻⁴ 0.695

In a preferred embodiment, the homopolymer and copolymer productsproduced by the present process may have an Mw of about 1,000 to about2,000,000 g/mol, alternately of about 30,000 to about 600,000 g/mol, oralternately of about 100,000 to about 500,000 g/mol, as determined byGPC and have a multi-modal, preferably bimodal, Mw/Mn.

End Uses

Articles made using polymers produced herein may include, for example,molded articles (such as containers and bottles, e.g., householdcontainers, industrial chemical containers, personal care bottles,medical containers, fuel tanks, and storage ware, toys, sheets, pipes,tubing) films, non-wovens, and the like. It should be appreciated thatthe list of applications above is merely exemplary, and is not intendedto be limiting.

Experimental

¹H NMR spectroscopic data were acquired at 250, 400, or 500 MHz usingsolutions prepared by dissolving approximately 10 mg of a sample inapproximately 0.75 mL of either C₆D₆, CD₂Cl₂, CDCl₃, or D₈-toluene. Thechemical shifts (δ) presented are relative to the residual protium inthe deuterated solvent at 7.15, 5.32, 7.24, and 2.09 for C₆D₆, CD₂Cl₂,CDCl₃, and D₈-toluene, respectively. For purposes of the claims 500 Mzand CD₂Cl₂ are used.

EXAMPLES

Complexes 1-5 have been prepared by reaction of intermediate A withsmall molecules containing reactive double or triple bonds. Dashed bondsto the metal center indicate an optional, dative bond.

HfBn₂Cl₂(Et₂O) was prepared by reaction of one equivalent of HfBn₄(Strem) with HfCl₄ (Strem) in ether for 5 hours followed by filtrationand crystallization of the product. (2,6-Diisopropylphenyl){mesityl[1-methyl-4-(2-methyl-1-benzothien-3-yl)-1H-imidazol-2-yl]methyl}amine(LH₂) was prepared as described in [Diamond, G. M.; Hall, K. A.;LaPointe, A. M.; Leclerc, M. K.; Longmire, J.; Shoemaker, J. A. W.; Sun,P. U.S. Pat. No. 7,256,296 for Symyx Technologies, Inc.; Diamond, G. M.;Hall, K. A.; LaPointe, A. M.; Leclerc, M. K.; Longmire, J.; Shoemaker,J. A. W.; Sun, P. ACS Catalysis 2011, 1, 887.]. Benzene (Merck) andhexane (Merck) were dried over and kept on over molecular sieves 4A.Dichloromethane (and CD₂Cl₂ for NMR measurements) was distilled overP₄O₁₀ and kept on molecular sieves 4A. Acetone (Merck),diisopropilcarbodiimide (Aldrich), dicyclohexylcarbodiimide (Aldrich),phenylisocyanate (Aldrich) and isobutyronitrile (Aldrich) were used asreceived.

Intermediate A

A mixture of(2,6-diisopropylphenyl){mesityl[1-methyl-4-(2-methyl-1-benzothien-3-yl)-1H-imidazol-2-yl]methyl}amine(LH₂) (1.06 g, 1.98 mmol) and HfCl₂Bn₂(Et₂O) (1.0 g, 1.98 mmol) wasdissolved in 300 ml of benzene, the formed solution was stirred for 3days in a pressure bottle at 80° C. Then solvent was evaporated, and theresidue was washed with hexane (20 ml) and dichloromethane (2×10 ml).Yield 850 mg (55%) of Intermediate A as white solid.

Anal. calc. for C₃₅H₃₉Cl₂HfN₃S: C, 53.68; H, 5.02; N, 5.37. Found: C,53.79; H, 5.29; N, 5.22.

¹H NMR (CD₂Cl₂): δ 8.45 (m, 1H, 7-H in benzothiophene), 7.80 (m, 1H, 5-Hin benzothiophene), 7.34 (m, 1H, 6-H in benzothiophene), 7.34 (s, 1H,5-H in imidazole), 7.20 (m, 2H, 3,5-H in in 2,6-diisopropylphenyl), 6.97(m, 1H, 4-H in in 2,6-diisopropylphenyl), 6.80 (m, 1H, 3-H in mesityl),6.67 (m, 1H, 5-H in mesityl), 6.13 (s, 1H, mesityl-CH), 3.22 (m, 1H,CHMe₂), 3.21 (s, 3H, NMe in imidazole), 3.20 (m, 1H, CHMe₂), 2.79 (s,3H, 2-Me in benzotiophene), 2.18 (s, 3H, 2-Me in mesityl), 2.00 (s, 3H,6-Me in mesityl), 1.57 (s, 3H, 4-Me in mesityl), 1.39 (d, J=6.65 Hz, 3H,CHMeMe′), 1.34 (d, J=6.85 Hz, 3H, CHMeMe′), 1.15 (d, J=6.65 Hz, 3H,CHMeMe′), 0.10 (d, J=6.65 Hz, 3H, CHMeMe′).

Example 1 Synthesis of Complex 1 (Cat ID=1)

A mixture of 200 mg (0.255 mmol) of Intermediate A and 15 mg (0.258mmol) of acetone in 15 ml of dichloromethane was stirred for 5 min atroom temperature. Further on, the solvent was evaporated, and theresidue was washed with 2×15 ml of hexane and dried in vacuum. Thisprocedure gave 185 mg (86%) of Complex 1 as a white solid.

Anal. calc. for C₃₈H₄₅Cl₂HfN₃OS: C, 54.25; H, 5.39; N, 4.99. Found: C,54.40; H, 5.61; N, 4.75.

¹H NMR (CD₂Cl₂): δ 7.77 (m, 1H, 7-H in benzothiophene), 7.48 (m, 1H, 5-Hin benzothiophene), 7.27, (m, 1H, 6-H in benzothiophene), 7.15 (m, 2H,3,5-H in 2,6-diisopropylphenyl), 6.92 (m, 1H, 4-H in2,6-diisopropylphenyl), 6.86 (s, 1H, 5-H in imidazole), 6.81 (m, 1H, 3-Hin mesityl), 6.64 (m, 1H, 5-H in mesityl), 5.96 (s, 1H, mesityl-CH),3.47 (m, 1H, CHMe₂), 3.21 (m, 1H, CHMe₂), 3.14 (s, 3H, NMe inimidazole), 2.50 (s, 3H, 2-Me in benzotiophene), 2.19 (s, 3H, MeMe′C—O),2.18 (s, 3H, MeMe′C—O), 1.85 (s, 3H, 2-Me in mesityl), 1.58 (s, 3H, 6-Mein mesityl), 1.48 (d, J=6.83 Hz, 6H, two CHMeMe′), 1.47 (s, J=6.24 Hz,3H, 4-Me in mesityl), 1.12 (d, 3H, J=6.83 Hz, CHMeMe′), 0.10 (d, J=6.83Hz, 3H, CHMeMe′).

¹³C{¹H} NMR (CD₂Cl₂): δ 155.50, 147.99, 147.53, 144.80, 143.85, 142.88,141.56, 140.46, 139.03, 138.66, 136.74, 135.51, 132.35, 131.08, 130.03,126.10, 124.13, 123.80, 123.68, 123.44, 122.97, 122.53, 84.76, 66.41,33.59, 33.35, 31.19, 28.86, 28.25, 26.98, 25.65, 25.08, 22.53, 21.29,20.76, 20.55, 16.83.

Example 2 Synthesis of Complex 2 (Cat ID=2)

A mixture of 200 mg (0.255 mmol) of Intermediate A and 33 mg (0.261mmol) of diisopropylcarbodiimide in 15 ml of in dichloromethane wasstirred for 5 min at room temperature. Further on, the solvent wasevaporated, and the residue was washed with 2×15 ml of hexane and driedin vacuum. This procedure gave 206 mg (89%) of Complex 2 as white solid.

Anal. calc. for C₄₂H₅₃Cl₂HfN₅S: C, 55.47; H, 5.87, N, 7.70. Found: C,55.39; H, 6.06; N, 7.50.

¹H NMR (CD₂Cl₂): δ 7.81 (m, 1H, 7-H in benzothiophene), 7.38 (m, 1H, 5-Hin benzothiophene), 7.24 (m, 2H, 3-H in 2,6-diisopropylphenyl), 7.13 (m,1H, 6-H in benzithiophene), 6.90 (m, 1H, 4-H in 2,6-diisopropylphenyl),6.76 (m, 1H, 3-H in mesityl), 6.69 (m, 1H, 5-H in imidazole), 6.57 (s,1H, 3-H in mesityl), 6,09 (s, 1H, mesityl-CH), 4.12 (m, 1H, CHMe₂), 3.97(m, 1H, Me₂CH—N), 3.57 (m, 1H, CHMe₂), 2.89 (s, 3H, NMe in imidazole),2.63 (s, 3H, 2-Me in benzotiophene), 2.42 (m, 1H, Me₂CH—N) 2.17, (s, 3H,2-Me in mesityl), 2.15 (s, 3H, 6-Me in mesityl), 1.45 (d, J=6.60 Hz, 3H,CHMeMe′), 1.43 (d, J=6.61 Hz, 3H, CHMeMe′), 1.42 (s, 3H, 4-Me inmesityl), 1.25 (d, J=6.61 Hz, 3H, N—CHMeMe′), 1.10 (d, J=6.97 Hz, 3H,CHMeMe′), 1.08 (d, J=6.60 Hz, 3H, N-CHMeMe′), 0.65 (d, J=6.24 Hz, 3H,N—CHMeMe′), 0.59 (d, 3H, J=6.60 Hz, N—CHMeMe′), 0.03 (d, J=6.97 Hz, 3H,CHMeMe′).

¹³C{¹H} NMR (CD₂Cl₂): δ 174.81, 159.68, 149.43, 149.11, 145.32, 143.06,139.95, 139.81, 138.73, 138.22, 137.37, 133.15, 132.99, 132.72, 129.71,129.39, 126.89, 125.81, 125.57, 124.97, 123.97, 123.87, 122.76, 122.72,65.14, 52.15, 50.76, 33.61, 29.16, 28.35, 28.09, 26.49, 26.10, 25.52,25.26, 22.28, 22.03, 21.33, 20.89, 20.70, 17.35, 14.29.

Example 3 Synthesis of Complex 3 (Cat ID=3)

A mixture of 200 mg (0.255 mmol) of Intermediate A and 53 mg (0.257mmol) dicyclohexylcarbodiimide in 15 ml of in dichloromethane wasstirred for 5 min at room temperature. Further on, the solvent wasevaporated, and the residue was washed with 2×15 ml of hexane and driedin vacuum. This procedure gave 214 mg (85%) of Complex 3 as a whitesolid.

Anal. calc. for C₄₈H₆₁Cl₂HfN₅S: C, 58.26; H, 6.21; N, 7.08. Found: C,58.43; H, 6.39; N, 6.85.

¹H NMR (CD₂Cl₂): δ 7.81 (m, 1H, 7-H in benzothiophene), 7.38 (m, 1H, 6-Hin benzothiophene), 7.22, (m, 2H, 3,5-H in 2,6-diisopropylphenyl), 7.12(m, 1H, 5-H in benzothiophene), 6.89 (m, 1H, 4-H in2,6-diisopropylphenyl), 6.76 (m, 1H, 3-H in mesityl), 6.66 (s, 1H, 5-Hin imidazole), 6.56 (s,1H, 3-H in mesityl), 6.08 (s, 1H, mesityl-CH),3.93 (m, 1H, CHMe₂), 3.67 (m, 1H, 1-H in cyclohexyl), 3.56 (m, 1H,CHMe₂), 2.90 (s, 3H, NMe in imidazole), 2.60 (s, 3H, 2-Me inbenzotiophene), 2.15, (s, 3H, 2-Me in mesityl), 2.14 (s, 3H, 6-Me inmesityl), 1.98 (m, 1H, 1-H in cyclohexyl), 1.88 (m, 2H, cyclohexyl),1.52-1.70 (m, 5H, cyclohexyl), 1.48 (d, J=6.84 Hz, 3H, CHMeMe′), 1.45(d, J 32 7.04 Hz, 3H, CHMeMe′), 1.44 (s, 3H, 4-Me in mesityl), 1.12-1.39(m, 6H, cyclohexyl), 1.07 (d, J=6.46 Hz, 3H, CHMeMe′), 0.63-1.02 (m, 5H,cyclohexyl), 0.43 (m, 1H, cyclohexyl), 0.30 (m, 1H, cyclohexyl), 0.01(d, J=6.84 Hz, 3H, CHMeMe′).

Example 4 Synthesis of Complex 4 (Cat ID=4)

A mixture of 200 mg (0.255 mmol) of Intermediate A and 31 mg (0.260mmol) of phenylisocyanate in 15 ml of in dichloromethane was stirred for5 min at room temperature. Further on, the solvent was evaporated, andthe residue was washed with 2×15 ml of hexane and dried in vacuum. Thisprocedure gave 180 mg (78%) of Complex 4 as a white solid.

Anal. calc. for C₄₂H₄₄Cl₂HfN₄OS: C, 55.91; H, 4.92; N, 6.21. Found: C,56.24; H, 5.17; N, 6.08.

¹H NMR (CD₂Cl₂): δ 7.72 (m, 1H, 7-H in benzothiophene), 7.24 (m, 2H,5,6-H in benzothiophene), 7.11-7.17 (m, 3H, 2,4,6-H in Ph-N═C),7.04-7.07 (m, 2H, 3,5-H in 2,6-diisopropylphenyl), 6.92 (m, 1H, 4-H in2,6-diisopropylphenyl), 6.86, (m, 1H, 5-H in imidazole), 6.83 (m, 1H,3-H in mesityl), 6.60 (m, 1H, 5-H in mesityl), 6.48 (m, 2H, 3,5-H inPh-N═C), 6.08 (s, 1H, mesityl-CH), 3.45 (m, 1H, CHMe₂), 3.07 (s, 3H, NMein imidazole), 3.02 (m, 1H, CHMe₂), 2.72 (s, 3H, 2-Me in benzotiophene),2.21 (s, 3H, 2-Me in mesityl), 2.17 (s, 3H, 6-Me in mesityl), 1.43 (s,3H, 4-Me in mesityl), 1.16 (d, J=6.65 Hz, 3H, CHMeMe′), 0.89 (d, J=6.85Hz, 3H, CHMeMe′), 0.74 (d, J=6.65 Hz, 3H, CHMeMe′), 0.09 (d, J=6.65 Hz,3H, CHMeMe′).

¹³C{¹H} NMR (CD₂C₂): δ 179.47, 159.09, 148.52, 146.06, 145.49, 144.93,144.15, 139.43, 139.36, 138.80, 138.44, 138.28, 132.90, 132.66, 131.64,130.01, 129.26, 126.96, 126.73, 126.14, 124.97, 124.89, 124.00, 123.94,123.80, 123.55, 122.25, 65.50, 34.07, 28.34, 28.30, 27.53, 25.82, 25.14,24.84, 22.22, 21.39, 20.72, 17.04.

Example 5 Synthesis of Complex 5 (Cat ID=5)

A mixture of 200 mg (0.255 mmol) of Intermediate A and 18 mg (0.261mmol) of isobutyronitrile in 15 ml of in dichloromethane was stirred for5 min at room temperature. Further on, the solvent was evaporated, andthe residue was washed with 2×15 ml of hexane and dried in vacuum. Thisprocedure gave 163 mg (75%) of Complex 5 as a white solid.

Anal. calc. for C₃₉H₄₆Cl₂HfN₄S: C, 54.96; H, 5.44; N, 6.57. Found: C,55.25; H, 5.30; N, 6.43.

¹H NMR (CD₂Cl₂): δ 7.79 (m, 1H, 5-H in benzothiophene), 7.37 (m, 1H, 7-Hin benzothiophene), 7.30 (m, 1H, 6-H in benzothiophene), 7.13-7.21 (m,2H, 3,5-H in 2,6-diisopropylphenyl), 6.92 (m, 1H, 4-H in2,6-diisopropylphenyl), 6.77 (m, 1H, 3-H in mesityl), 6.76 (s, 1H, 5-Hin imidazole), 6.61 (s,1H, 3-H in mesityl), 6,05 (s, 1H, mesityl-CH),3.80 (m, 1H, N═CCHMe₂), 3.37 (m, 1H, CHMe₂), 3.21 (m, 1H, CHMe₂), 3.10(s, 3H, NMe in imidazole), 2.42 (s, 3H, 2-Me in benzotiophene), 2.16,(s, 3H, 2-Me in mesityl), 2.09 (s, 3H, 6-Me in mesityl), 1.65 (s, 3H,4-Me in mesityl), 1.50 (d, J=6.88 Hz, 3H, CHMeMe′), 1.40 (d, J=6.69 Hz,3H, CHMeMe′), 1.22 (d, J=6.48 Hz, 3H, N═CCHMeMe′), 1,13 (d, J=6.69 Hz,3H, CHMeMe′), 0.83 (d, J=6.89 Hz, 3H, N═CCHMeMe′), 0.18 (d, J=6.69 Hz,3H, CHMeMe′).

¹³C{¹H} NMR (CD₂Cl₂): δ 183.34, 157.61, 148.49, 146.11, 145.91, 143.52,142.15, 139.50, 139.01, 138.92, 138.45, 136.96, 132.81, 132.57, 131.28,129.86, 126.51, 124.80, 123.86, 123.59, 123.49, 123.37, 122.96, 122.51,65.96, 39.30, 33.51, 28.70, 28.07, 26.72, 26.61, 25.41, 22.35, 21.80,20.71, 20.55, 20.28, 20.11, 15.84.

Polymerization Examples

Solutions of the pre-catalysts (Complexes 1 through 5, prepared above)were made using toluene (ExxonMobil Chemical—anhydrous, stored under N₂)(98%). Pre-catalyst solutions were typically 0.5 mmol/L. Solvents,polymerization grade toluene and/or isohexanes were supplied byExxonMobil Chemical Co. and are purified by passing through a series ofcolumns: two 500 cc Oxyclear cylinders in series from Labclear (Oakland,Calif.), followed by two 500 cc columns in series packed with dried 3 Åmole sieves (8-12 mesh; Aldrich Chemical Company), and two 500 cccolumns in series packed with dried 5 Å mole sieves (8-12 mesh; AldrichChemical Company).

1-octene (98%) (Aldrich Chemical Company) was dried by stirring over NaKovernight followed by filtration through basic alumina (Aldrich ChemicalCompany, Brockman Basic 1).

Polymerization grade ethylene was used and further purified by passingit through a series of columns: 500 cc Oxyclear cylinder from Labclear(Oakland, Calif.) followed by a 500 cc column packed with dried 3 Å molesieves (8-12 mesh; Aldrich Chemical Company), and a 500 cc column packedwith dried 5 | mole sieves (8-12 mesh; Aldrich Chemical Company).

Polymerization grade propylene was used and further purified by passingit through a series of columns: 2250 cc Oxiclear cylinder from Labclearfollowed by a 2250 cc column packed with 3 Å mole sieves (8-12 mesh;Aldrich Chemical Company), then two 500 cc columns in series packed with5 Å mole sieves (8-12 mesh; Aldrich Chemical Company), the a 500 cccolumn packed with Selexsorb CD (BASF), and finally a 500 cc columnpacked with Selexsorb COS (BASF).

Activation of the pre-catalysts was by methylalumoxane (MAO, 10 wt % intoluene, Albemarle Corp.) MAO was used as a 0.5 wt % or 0.75 wt % intoluene solution. Micromoles of MAO reported in the experimental sectionare based on the micromoles of aluminum in MAO. The formula weight ofMAO is 58.0 grams/mole.

Reactor Description and Preparation:

Polymerizations were conducted in an inert atmosphere (N₂) drybox usingautoclaves equipped with an external heater for temperature control,glass inserts (internal volume of reactor=23.5 mL for C₂ and C₂/C₈ runs;22.5 mL for C₃ runs), septum inlets, regulated supply of nitrogen,ethylene and propylene, and equipped with disposable PEEK mechanicalstirrers (800 RPM). The autoclaves were prepared by purging with drynitrogen at 110° C. or 115° C. for 5 hours and then at 25° C. for 5hours.

Ethylene Polymerization (PE) or Ethylene/1-octene Copolymerization (EO):

The reactor was prepared as described above, and then purged withethylene. For MAO activated runs, toluene, 1-octene (100 μL when used),and activator (MAO) were added via syringe at room temperature andatmospheric pressure. The reactor was then brought to processtemperature (80° C.) and charged with ethylene to process pressure (75psig=618.5 kPa or 200 psig=1480.3 kPa) while stirring at 800 RPM. Thepre-catalyst solution was then added via syringe to the reactor atprocess conditions. Ethylene was allowed to enter (through the use ofcomputer controlled solenoid valves) the autoclaves duringpolymerization to maintain reactor gauge pressure (+/−2 psig). Reactortemperature was monitored and typically maintained within+/−1° C.Polymerizations were halted by addition of approximately 50 psi O₂/Ar (5mole % O₂) gas mixture to the autoclaves for approximately 30 seconds.The polymerizations were quenched after a predetermined cumulativeamount of ethylene had been added or for a maximum of 30 minutespolymerization time. The reactors were cooled and vented. The polymerwas isolated after the solvent was removed in-vacuo. The finalconversion (quench value in psi) of ethylene added/consumed is reportedin the Tables 1(PE) and 2 (EO), in addition to the quench time for eachrun. Yields reported include total weight of polymer and residualcatalyst. Catalyst activity is reported as grams of polymer per mmoltransition metal compound per hour of reaction time (g/mmol·hr).

Propylene Polymerization:

The reactor was prepared as described above, then heated to 40° C. andthen purged with propylene gas at atmospheric pressure. For MAOactivated runs, toluene, MAO, and liquid propylene (1.0 mL) were addedvia syringe. The reactor was then heated to process temperature (70° C.or 100° C.) while stirring at 800 RPM. The pre-catalyst solution wasadded via syringe with the reactor at process conditions. Reactortemperature was monitored and typically maintained within+/−1° C.Polymerizations were halted by addition of approximately 50 psi O₂/Ar (5mole % O₂) gas mixture to the autoclaves for approximately 30 seconds.The polymerizations were quenched based on a predetermined pressure lossof approximately 8 psi or for a maximum of 30 minutes polymerizationtime. The reactors were cooled and vented. The polymer was isolatedafter the solvent was removed in-vacuo. The quench time (s) and quenchvalue (psi) are reported in Table 3 for each run. Yields reportedinclude total weight of polymer and residual catalyst. Catalyst activityis reported as grams of polymer per mmol transition metal compound perhour of reaction time (g/mmol·hr).

Polymer Characterization

For analytical testing, polymer sample solutions were prepared bydissolving polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity fromSigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%from Aldrich) at 165° C. in a shaker oven for approximately 3 hours. Thetypical concentration of polymer in solution was between 0.1 to 0.9mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB. Samples werecooled to 135° C. for testing.

High temperature size exclusion chromatography was performed using anautomated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816;6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409;6,454,947; 6,260,407; and 6,294,388; each of which is incorporatedherein by reference. Molecular weights (weight average molecular weight(Mw) and number average molecular weight (Mn)) and molecular weightdistribution (MWD=Mw/Mn), which is also sometimes referred to as thepolydispersity (PDI) of the polymer, were measured by Gel PermeationChromatography using a Symyx Technology GPC equipped with evaporativelight scattering detector and calibrated using polystyrene standards(Polymer Laboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw)between 5000 and 3,390,000). Samples (250 μL of a polymer solution inTCB were injected into the system) were run at an eluent flow rate of2.0 mL/minute (135° C. sample temperatures, 165° C. oven/columns) usingthree Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5mm columns inseries. No column spreading corrections were employed. Numericalanalyses were performed using Epoch® software available from SymyxTechnologies or Automation Studio software available from Freeslate. Themolecular weights obtained are relative to linear polystyrene standards.Molecular weight data is reported in Tables 1, 2, and 3.

Differential Scanning calorimetry (DSC) measurements were performed on aTA-Q100 instrument to determine the melting point of the polymers.Samples were pre-annealed at 220° C. for 15 minutes and then allowed tocool to room temperature overnight. The samples were then heated to 220°C. at a rate of 100° C./minute and then cooled at a rate of 50°C./minute. Melting points were collected during the heating period. Theresults are reported in the Tables 1, 2 and 3 as T_(m) (° C.).

Samples for infrared analysis were prepared by depositing the stabilizedpolymer solution onto a silanized wafer (Part number S10860, Symyx). Bythis method, approximately between 0.12 and 0.24 mg of polymer isdeposited on the wafer cell. The samples were subsequently analyzed on aBrucker Equinox 55 FTIR spectrometer equipped with Pikes' MapplRspecular reflectance sample accessory. Spectra, covering a spectralrange of 5000 cm⁻¹ to 500 cm⁻¹, were collected at a 2 cm⁻¹ resolutionwith 32 scans.

For ethylene-1-octene copolymers, the wt % copolymer was determined viameasurement of the methyl deformation band at ˜1375 cm⁻¹. The peakheight of this band was normalized by the combination and overtone bandat ˜4321 cm⁻¹, which corrects for path length differences. Thenormalized peak height was correlated to individual calibration curvesfrom ¹H NMR data to predict the wt % copolymer content within aconcentration range of ˜2 to 35 wt % for octene. Typically, R²correlations of 0.98 or greater are achieved. These numbers are reportedin Table 2 under the heading C8 wt %). Reported values below 4.1 wt %are outside the calibration range.

Polymerization results are collected in Tables 1, 2, and 3 below. “Ex#”stands for example number. “Cat ID” identifies the pre-catalyst used inthe experiment. Corresponding numbers identifying the pre-catalyst arelocated in the synthetic experimental section. “Catalyst (μmol)” is theamount of pre-catalyst added to the reactor. “Yield” is polymer yield,and is not corrected for catalyst residue. “Quench time (s)” is theactual duration of the polymerization run in seconds. “Quench Value(psi)” for ethylene based polymerization runs is the set maximum amountof ethylene uptake (conversion) for the experiment. If a polymerizationquench time is 30 minutes or less, then the polymerization ran until theset maximum value of ethylene uptake was reached. For propylene basedpolymerization runs, quench value indicates the pressure loss(conversion) of propylene during the polymerization.

TABLE 1 Summary of conditions and polymer characterization data forethylene homopolymerizations performed with complexes 1-5. Activity Catquench yield (g P/mmol Mn Mw T_(m) Ex# ID time (s) (g) cat · hr) (g/mol)(g/mol) Mw/Mn (° C.) PE-1 1 200 0.068 48,960 181,283 692,175 3.82 134.7PE-2 1 229 0.070 44,017 153,626 717,955 4.67 134.8 PE-3 1 229 0.06238,987 193,541 702,713 3.63 134.7 PE-4 2 359 0.115 46,128 227,572864,469 3.80 135.5 PE-5 2 349 0.123 50,751 286,657 945,980 3.30 135.6PE-6 2 336 0.122 52,286 221,873 871,766 3.93 135.5 PE-7 3 496 0.06819,742 242,998 975,974 4.02 134.9 PE-8 3 405 0.061 21,689 229,327951,915 4.15 134.6 PE-9 3 360 0.053 21,200 288,840 1,019,985 3.53 134.5PE-10 4 754 0.041 7,830 145,481 867,607 5.96 134.6 PE-11 4 633 0.0439,782 131,914 871,964 6.61 PE-12 4 728 0.049 9,692 173,515 973,586 5.61134.7 PE-13 5 301 0.073 34,924 90,354 223,981 2.48 134.8 PE-14 5 2650.076 41,298 88,473 226,519 2.56 135.0 PE-15 5 271 0.081 43,041 102,560246,122 2.40 135.1 Reactor conditions: Pre-catalyst used at 0.025 umoland activated with 500 equivalents of MAO; 80° C. reactor temperature;75 psid ethylene; 5.0 ml toluene; 800 rpm stir speed; reactor quenchedat 20 psid ethylene (quench value) uptake or at a maximum time limit of30 minutes.

TABLE 2 Summary of conditions and polymer characterization data forethylene- octene copolymerizations performed with complexes 1-5.Activity Cat C3 quench yield (g P/mmol Mn Mw C8 T_(m) Ex# ID (psig) time(s) (g) cat · hr) (g/mol) (g/mol) Mw/Mn wt %* (° C.) EO-1 1 75 474 0.04313,063 119,134 260,849 2.19 3.8 123.8 EO-2 1 75 426 0.044 14,873 131,467270,744 2.06 3.4 123.7 EO-3 1 75 449 0.044 14,111 112,870 367,430 3.263.1 123.6 EO-4 1 200 312 0.120 55,385 235,808 650,915 2.76 1.7 126.9EO-5 1 200 363 0.125 49,587 266,855 751,873 2.82 1.4 127.3 EO-6 1 200314 0.103 47,236 235,014 774,672 3.3 1.4 127.4 EO-7 2 75 395 0.04917,863 128,382 439,784 3.43 4.7 123.1 EO-8 2 75 557 0.050 12,926 186,930476,804 2.55 5.8 122.9 EO-9 2 75 662 0.052 11,311 203,443 517,716 2.544.6 123.4 EO-10 2 200 326 0.111 49,031 285,668 911,327 3.19 2.8 125.5EO-11 2 200 371 0.110 42,695 230,224 828,387 3.6 2.4 125.8 EO-12 2 200419 0.115 39,523 292,098 912,119 3.12 2.5 124.9 EO-13 3 75 808 0.0488,554 202,556 848,970 4.19 3.4 124.1 EO-14 3 75 588 0.038 9,306 184,471683,615 3.71 3.1 124.1 EO-15 3 75 725 0.045 8,938 242,752 1,000,663 4.123.4 123.9 EO-16 3 200 672 0.058 12,429 362,575 1,224,852 3.38 1.1 127.9EO-17 3 200 509 0.057 16,126 500,557 1,417,445 2.83 1.3 127.9 EO-18 3200 1800 0.006 480 EO-19 4 75 986 0.046 6,718 157,029 660,140 4.2 8.6119.0 EO-20 4 75 1290 0.040 4,465 120,442 791,286 6.57 8.2 119.2 EO-21 475 1091 0.036 4,752 139,383 663,959 4.76 6.7 118.9 EO-22 4 200 646 0.05612,483 185,963 858,186 4.61 2.6 EO-23 4 200 682 0.066 13,935 263,198934,290 3.55 3.0 123.4 EO-24 4 200 536 0.060 16,119 281,531 1,129,5374.01 4.0 124.2 EO-25 5 75 252 0.081 46,286 118,641 279,745 2.36 10.8114.9 EO-26 5 75 244 0.077 45,443 107,403 261,693 2.44 13.5 114.9 EO-275 75 229 0.089 55,965 EO-28 5 200 167 0.124 106,922 169,782 374,760 2.213.1 122.8 EO-29 5 200 173 0.110 91,561 178,039 364,060 2.04 2.5 123.5EO-30 5 200 196 0.109 80,082 159,358 359,119 2.25 3.9 122.8 Reactorconditions: Pre-catalyst used at 0.025 umol and activated with 500equivalence of MAO; 80° C. reactor temperature; 100 uL 1-octene; 4.9 mltoluene; 800 rpm stir speed; reactor quenched at 20 psid ethylene(quench value) uptake for runs at 75 psid ethylene or 15 psid ethyleneuptake for runs at 200 psid ethylene, or at a maximum time limit of 30minutes. *wt % octene less than 4.1 wt % was outside the calibrationrange for the FTIR.

TABLE 3 Summary of conditions and polymer characterization data forpropylene polymerizations performed with complexes 1-5. Activity CatCatalyst T quench yield (g P/mmol Mn Mw T_(m) Ex# ID (umol) (C.) time(s) (g) cat · hr) (g/mol) (g/mol) Mw/Mn (° C.) PP-1 1 0.04 70 1800 0.005250 PP-2 1 0.04 70 1801 0.005 250 PP-3 1 0.04 70 1801 0.004 200 PP-4 10.04 100 1801 0.004 200 PP-5 1 0.04 100 1801 0.005 250 PP-6 1 0.04 1001801 0.005 250 PP-7 2 0.04 70 1801 0.003 150 PP-8 2 0.04 70 1800 0.003150 PP-9 2 0.04 70 1800 0.003 150 PP-10 2 0.04 100 1801 0.003 150 PP-112 0.04 100 1801 0.004 200 PP-12 2 0.04 100 1801 0.003 150 PP-13 3 0.0870 1800 0.007 175 PP-14 3 0.08 70 1801 0.007 175 PP-15 3 0.08 70 18010.007 175 PP-16 3 0.08 100 1801 0.007 175 PP-17 3 0.08 100 1801 0.007175 PP-18 3 0.08 100 1801 0.007 175 PP-19 4 0.08 70 1804 0.036 89829,701 249,087 8.39 138.6 PP-20 4 0.08 70 1800 0.037 925 20,538 265,55412.93 138.9 PP-21 4 0.08 70 1801 0.034 850 36,935 272,014 7.36 139.2PP-22 4 0.08 100 1801 0.035 875 11,892 81,342 6.84 139.6 PP-23 4 0.08100 1802 0.034 849 10,992 77,487 7.05 139.6 PP-24 4 0.08 100 1800 0.032800 10,681 65,463 6.13 139.8 PP-25 5 0.08 70 433 0.079 8,210 23,65454,480 2.30 131.4 PP-26 5 0.08 70 490 0.091 8,357 25,103 60,456 2.41126.5 PP-27 5 0.08 70 477 0.096 9,057 27,961 61,642 2.20 132.1 PP-28 50.08 100 103 0.174 76,019 22,215 49,730 2.24 125.6 PP-29 5 0.08 100 1040.173 74,856 17,709 47,674 2.69 119.9 PP-30 5 0.08 100 103 0.171 74,70912,833 47,411 3.69 125.0 Pre-catalyst activated with 500 equivalence ofMAO; 5.1 ml toluene; 1.0 ml C3; 800 rpm stir speed; reactor quenched at8 psid pressure loss (quench value) or at a maximum time limit of 30minutes. Catalysts 4 and 5 produced isotactic polypropylene.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including.” Likewise, whenever a composition,an element, or a group of elements is preceded with the transitionalphrase “comprising,” it is understood that we also contemplate the samecomposition or group of elements with transitional phrases “consistingessentially of,” “consisting of,” “selected from the group of consistingof,” or “is” preceding the recitation of the composition, element, orelements and vice versa.

What is claimed is:
 1. A transition metal compound formed by thechelation of a tridentate dianionic heterocyclic amido ligand to a group3, 4, or 5 transition metal, where the tridentate ligand coordinates tothe metal forming a five-membered ring and an eight-membered ring.
 2. Aheterocyclic amido transition metal complex represented by the formula(A) or (B):

wherein: M is a Group 3, 4, or 5 metal; Q¹ is a group that links R² andR³ by a three atom bridge represented by the formula: -G¹-G²-G³- whereG² is a group 15 or 16 atom that forms a dative bond to M, G¹ and G³ areeach a group 14 atom that are joined together by two or three additionalgroup 14, 15, or 16 atoms to form a heterocycle or substitutedheterocycle; Q² is a group that forms an anionic bond with M, said Q²group being selected from O, S, CH₂, CHR¹⁷, C(R¹⁷)₂, NR¹⁷ or PR¹⁷, whereeach R¹⁷ is independently selected from hydrogen, halogen, hydrocarbyls,substituted hydrocarbyls, halocarbyls, substituted halocarbyls,silylcarbyls, and polar groups; Q³ is -(TT)- or -(TTT)-, where each T isa substituted or unsubstituted group 14, 15, or 16 element so thattogether with the “—C—N═C—” fragment it forms a 5- or 6-memberedheterocycle or substituted heterocycle; R¹ is selected fromhydrocarbyls, substituted hydrocarbyls, halocarbyls, substitutedhalocarbyls, and silylcarbyls; R² is -E(R¹²)(R¹³)— where E is carbon,silicon, or germanium, and each R¹² and R¹³ is independently selectedfrom the group consisting of hydrogen, halogen, hydrocarbyls,substituted hydrocarbyls, halocarbyls, substituted halocarbyls,silylcarbyls, substituted and polar groups; R³ is either C or N, and R⁴and R⁵ are C, and R³ and R⁴ are part of a five or six-memberedcarbocyclic or heterocyclic ring, which may be substituted orunsubstituted, and R⁴ and R⁵ are part of a five or six-memberedcarbocyclic or heterocyclic ring, which may be substituted orunsubstituted; each J is independently selected from C, CH, CH₂, CR¹⁸,CHR¹⁸, C(R¹⁸)₂, Si(R¹⁸)₂, SiH(R¹⁸), NH, NR¹⁸, O, or S, where R¹⁸ isselected from hydrocarbyls, substituted hydrocarbyls, halocarbyls,substituted halocarbyls, halogen, and silylcarbyls; each x isindependently 3 or 4 representing the number of J groups linked togetherin series; Y is selected from substituted and unsubstituted group 14elements; L is an anionic leaving group, where the L groups may be thesame or different and any two L groups may be linked to form a dianionicleaving group; L′ is neutral Lewis base; n is 1, 2, or 3; w is 0, 1, 2,or 3; wherein n+w is not greater than 4; and wherein the tridentatedianionic ligand is chelated to the metal M in such a fashion that thecomplex features an eight-membered chelate ring and a five-memberedchelate ring, which are indicated in the formulas (A) and (B) by thenumbers 8 and 5, respectively.
 3. The complex of claim 2 wherein Q² isCH₂, CHMe, CHEt, CHBu, CH(pentyl), CH(hexyl), CH(hexyl), CH(octyl),CH(nonyl), CH(decyl), or CHPh, O, N(Ph), N(Mesityl),N(2,6-dimethylphenyl), N(2,6-diethylphenyl), N(2-methylphenyl),N(2-ethylphenyl), N(butyl), N(propyl), N(isopropyl), N(cyclohexyl),N(t-butyl), or N(2,6-diisopropylphenyl).
 4. The complex of claim 2,wherein Q² and Y are each independently CH₂ or CH(hydrocarbyl), whereeach hydrocarbyl groups contains 1 to 20 carbon atoms.
 5. The complex ofclaim 2 wherein Q² is not CH₂, CH(hydrocarbyl), or C(hydrocarbyl)₂,where the hydrocarbyl groups are independently selected from groups thatcontain 1 to 20 carbon atoms
 6. A heterocyclic amido transition metalcomplex represented by the formula (C) or (D):

wherein: M is a Group 3, 4, or 5 metal; Q¹ is a group that links R² andR³ by a three atom bridge represented by the formula: -G¹-G²-G³- whereG² is a group 15 or 16 atom that forms a dative bond to M, G¹ and G³ areeach a group 14 atom that are joined together by two or three additionalgroup 14, 15, or 16 atoms to form a heterocycle or substitutedheterocycle; Q²′ is a group that forms an anionic bond with M, said Q²group being selected from N, P, CH, CR¹⁷, where each R¹⁷ isindependently selected from hydrogen, halogen, hydrocarbyls, substitutedhydrocarbyls, halocarbyls, substituted halocarbyls, silylcarbyls, andpolar groups; Q³ is -(TT)- or -(TTT)-, where each T is a substituted orunsubstituted group 14, 15, or 16 element so that together with the“—C—N═C—” fragment it forms a 5- or 6-membered heterocycle orsubstituted heterocycle; R¹ is selected from hydrocarbyls, substitutedhydrocarbyls, halocarbyls, substituted halocarbyls, and silylcarbyls; R²is -E(R¹²)(R¹³)— where E is carbon, silicon, or germanium, and each R¹²and R¹³ is independently selected from the group consisting of hydrogen,halogen, hydrocarbyls, substituted hydrocarbyls, halocarbyls,substituted halocarbyls, silylcarbyls, substituted and polar groups; R³is either C or N, and R⁴ and R⁵ are C, and R³ and R⁴ are part of a fiveor six-membered carbocyclic or heterocyclic ring, which may besubstituted or unsubstituted, and R⁴ and R⁵ are part of a five orsix-membered carbocyclic or heterocyclic ring, which may be substitutedor unsubstituted; each J is independently selected from C, CH, CH₂,CR¹⁸, CHR¹⁸, C(R¹⁸)₂, Si(R¹⁸)₂, SiH(R¹⁸), NH, NR¹⁸, O, or S, where R¹⁸is selected from hydrocarbyls, substituted hydrocarbyls, halocarbyls,substituted halocarbyls, halogen, and silylcarbyls; each x isindependently 3 or 4 representing the number of J groups linked togetherin series; Y′ is selected from substituted and unsubstituted group 14elements; L is an anionic leaving group, where the L groups may be thesame or different and any two L groups may be linked to form a dianionicleaving group; L′ is neutral Lewis base; n is 1, 2, or 3; w is 0, 1, 2,or 3; wherein n+w is not greater than 4; and wherein the tridentatedianionic ligand is chelated to the metal M in such a fashion that thecomplex features an eight-membered chelate ring and a five-memberedchelate ring, which are indicated in the formulas (A) and (B) by thenumbers 8 and 5, respectively.
 7. The complex of claim 2, wherein M isTi, Zr, or Hf.
 8. The complex of claim 2, wherein R² is represented bythe formula:

where R¹² is hydrogen, alkyl, aryl, or halogen; and R¹³ is hydrogen,alkyl, aryl, or halogen.
 9. The complex of claim 2, wherein R¹ isselected from phenyl groups that are substituted with 0, 1, 2, 3, 4, or5 substituents selected from the group consisting of F, Cl, Br, I, CF₃,NO₂, alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10carbons.
 10. The complex of claim 2, wherein each J is selected from C,CH, CH₂, Si(R¹⁸)₂, SiH(R¹⁸), NR¹⁸, O, or S, where R¹⁸ is selected fromhydrocarbyls, substituted hydrocarbyls, and silylcarbyls.
 11. Thecomplex of claim 2, wherein the complex is represented by the formula:

wherein: M, R¹, R², L, L′, n, w, Y, and Q² are defined in claim 2; E²and E³ are independently selected from O, S, NH, or NR⁹, where R⁹ is ahydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, halogen, silylcarbyl, or polar group; each R⁷ isindependently selected from hydrogen, halogen, hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, and polargroups; each R⁸ is independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, and polar groups.
 12. The complex of claim 2,wherein the complex is represented by the formula:

wherein M, R¹, R², L, L′, n, w, Y, and Q² are defined in claim 2; E² isselected from O, S, NH, or NR⁹, where R⁹ is a hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, halogen, silylcarbyl,or polar group; each R⁷ is independently selected from hydrogen,halogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, and polar groups; each R⁸ is independentlyselected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, and polar groups. 13.The complex of claim 2, wherein the complex is represented by theformula:

wherein M, R¹, R², L, L′, n, w, Y, and Q² are defined in claim 2; E² isselected from O, S, NH, or NR⁹, where R⁹ is a hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, halogen, silylcarbyl,or polar group; each R⁸ is independently selected from hydrogen,halogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, and polar groups.
 14. The complex of claim 6,wherein the complex is represented by the formula:

M, R¹, R², L, L′, n, w, R¹⁷, and R¹⁸ are as defined in claim 6; Y′ is CHor C(R¹⁸); Q²′is selected from N, P, CH, or CR¹⁷; E² and E³ areindependently selected from O, S, NH, or NR⁹, where R⁹ is a hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl, halogen,silylcarbyl, or polar group; each R⁷ is independently selected fromhydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, silylcarbyl, and polar groups; each R⁸ isindependently selected from hydrogen, halogen, hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, and polargroups.
 15. The complex of claim 6, wherein the complex is representedby the formula:

M, R², L, L′, n, w, R¹⁷, and R¹⁸ are as defined in claim 6; Y′ is CH orC(R¹⁸); Q²′is selected from N, P, CH, or CR¹⁷; E² is independentlyselected from O, S, NH, or NR⁹, where R⁹ is a hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, halogen, silylcarbyl,or polar group; each R⁷ is independently selected from hydrogen,halogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, and polar groups; each R⁸ is independentlyselected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, and polar groups. 16.The complex of claim 6, wherein the complex is represented by theformula:

M, R¹, R², L, n, w, R¹⁷, and R¹⁸ are as defined in claim 6; Y′ is CH orC(R¹⁸); Q² is selected from N, P, CH, or CR¹⁷; E² is selected from O, S,NH, or NR⁹, where R⁹ is a hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, halogen, silylcarbyl, or polargroup; each R⁸ is independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, and polar groups.
 17. A catalyst systemcomprising an activator and the heterocyclic amido transition metalcomplex of claim
 1. 18. A catalyst system comprising an activator andthe heterocyclic amido transition metal complex of claim
 2. 19. Thecatalyst system of claim 17 wherein the activator comprises anon-coordinating anion and/or an alumoxane.
 20. The catalyst system ofclaim 17, wherein the catalyst system is supported.
 21. The catalystsystem of claim 17, wherein M is Hf or Zr.
 22. A polymerization processto produce polyolefin comprising contacting one or more olefin monomerswith the catalyst system of claim 17 and recovering olefin polymer. 23.The process of claim 22, wherein the monomer comprises ethylene.
 24. Theprocess of claim 22, wherein the monomer comprises propylene.
 25. Theprocess of claim 22, wherein the process is a solution process.
 26. Theprocess of claim 22, wherein the process is a gas phase or slurryprocess.
 27. The process of claim 18, wherein the process is a gas phaseor slurry process.